METHOD FOR PREPARING SILAHYDROCARBONS

Abstract

The present disclosure is directed to a process for preparing silahydrocarbons of formula (I):

##STR00001##

the process including the step of reacting a compound of formula (II):

R.sup.1-MX(II)

with a compound of formula (III):

##STR00002##

as well as to silahydrocarbons prepared by such a process, and to compositions and articles of manufacture containing such silahydrocarbons.

Claims

1. A process for preparing a compound of formula (I): ##STR00110## comprising the step of reacting a compound of formula (II):
R.sup.1-MX(II) wherein M is Zn or Mg; R.sup.1 is an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, or heteroaryl group, each of which is optionally substituted with one or more substituents, wherein at least one of the one or more substituents is optionally a moiety of formula -MX, wherein M is Zn or Mg and X is Cl, Br, or I; and X is Cl, Br, or I, or, when R.sup.1 is an alkyl group, X is optionally an alkyl group identical to that of R.sup.1; with a compound of formula (III): ##STR00111## wherein X is Cl, Br, I, OS(O).sub.2alkyl, OS(O).sub.2perfluoroalkyl, or OS(O).sub.2aryl; and R.sup.2, R.sup.3, and R.sup.4 are, independently, selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl group is optionally substituted with one or more substituents, Cl, Br, I, OS(O).sub.2alkyl groups, OS(O).sub.2perfluoroalkyl groups, and OS(O).sub.2aryl groups, wherein at least one of the one or more substituents is optionally a moiety of formula SiR.sup.5R.sup.6X, wherein R.sup.5 and R.sup.6 are each, independently, selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl, each of which is optionally substituted with one or more substituents, and X is Cl, Br, I, OS(O).sub.2alkyl, OS(O).sub.2perfluoroalkyl, or OS(O).sub.2aryl; and wherein R.sup.2, R.sup.3, and/or R.sup.4, when taken together, optionally define an optionally substituted ring system; in the presence of a catalyst comprising a Group 8, 9, or 10 transition metal, a ligand, a solvent, and, optionally, an additive; wherein R.sup.2, R.sup.3, and/or R.sup.4 are optionally covalently linked to R.sup.1; and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 of the compound of formula (I) are as defined above.

2. The process of claim 1, wherein R.sup.1 is sterically hindered.

3. The process of claim 1, wherein R.sup.1 is selected from the group consisting of primary, secondary, and tertiary alkyl groups, primary, secondary and tertiary alkenyl groups, and primary, secondary and tertiary alkynyl groups, each of which is optionally substituted.

4. The process of claim 1, wherein one or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is substituted with a least one silyl group.

5. The process of claim 1, wherein R.sup.2 is selected from the group consisting of Cl, Br, I, OS(O).sub.2alkyl groups, OS(O).sub.2perfluoroalkyl groups, and OS(O).sub.2aryl groups.

6. The process of claim 5, wherein X and R.sup.2 are both Cl.

7. The process of claim 1, wherein R.sup.3 is selected from the group consisting of Cl, Br, I, OS(O).sub.2alkyl groups, OS(O).sub.2perfluoroalkyl groups, and OS(O).sub.2aryl groups.

8. The process of claim 1, wherein X, R.sup.2, and R.sup.3 are all Cl.

9. The process of claim 1, wherein R.sup.4 is selected from the group consisting of Cl, Br, I, OS(O).sub.2alkyl groups, OS(O).sub.2perfluoroalkyl groups, and OS(O).sub.2aryl groups.

10. The process of claim 1, wherein the Group 8, 9, or 10 transition metal is selected from the group consisting of Pd, Ni, Co, Rh, and Ir.

11. The process of claim 1, wherein the catalyst comprises Pd and is selected from the group consisting of Pd(OAc).sub.2, PdBr.sub.2, PdI.sub.2, Pd(dba).sub.2, Pd(dba).sub.3, [allylPdCl].sub.2, Pd.sub.2dba.sub.3.CHCl.sub.3, [(3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P].sub.2PdI.sub.2, [(3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P].sub.2PdCl.sub.2, (COD)Pd(CH.sub.2TMS).sub.2, (COD)PdCl.sub.2, (PPh.sub.3).sub.2PdCl.sub.2, (PPh.sub.3).sub.4Pd, (MeCN).sub.2PdCl.sub.2, and (IPr).sub.2PdCl.sub.2.

12. The process of claim 1, wherein the catalyst comprises Ni and is selected from the group consisting of Ni halides, Ni halide solvent complexes, and Ni(COD).sub.2.

13. The process of claim 1, wherein the ligand is selected from the group consisting of phosphine ligands, arsine ligands, nitrogen-containing ligands, and N-heterocyclic carbene ligands.

14. The process of claim 1, wherein the ligand is selected from the group consisting of PPh.sub.3, (3,5-t-BuC.sub.6H.sub.3).sub.2P(tBu), Ph.sub.2P(tBu), PhP(t-Bu).sub.2, (3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P, (4-MeOC.sub.6H.sub.4).sub.3P, (t-Bu).sub.3P, (t-Bu).sub.2PCy, (t-Bu)PCy.sub.2, Cpy.sub.3P, Cy.sub.2PMe, Cy.sub.2PEt, Cy.sub.3P, (o-tol).sub.3P, (furyl).sub.3P, (4-FC.sub.6H.sub.4).sub.3P, (4-CF.sub.3C.sub.6H.sub.4).sub.3P, BIPHEP, NapthPhos, XantPhos, dppf, dppe, dppb, dpppe, dcpe, dcpp, dcpb, SPhos, XPhos, DavePhos, JohnPhos, BrettPhos, QPhos, AmgenPhos, RockPhos, RuPhos, VPhos, tBuXPhos, tBuBrettPhos, TrixiePhos, AZPhos, CPhos, (3,5-t-BuC.sub.6H.sub.3).sub.2P(iPr), (3,5-t-BuC.sub.6H.sub.3).sub.2P(Et), (3,5-t-BuC.sub.6H.sub.3).sub.2P(Me), (3,5-i-PrC.sub.6H.sub.3).sub.2P(tBu), (3,5-i-PrC.sub.6H.sub.3).sub.2P(iPr), (3,5-i-PrC.sub.6H.sub.3).sub.2P(Et), (3,5-i-PrC.sub.6H.sub.3).sub.2P(Me), (3,5-t-Bu-4-MeOC.sub.6H.sub.2).sub.2P(tBu), (3,5-t-Bu-4-MeOC.sub.6H.sub.2).sub.3P, BINAP, SIPr, IPr, IMes, ISMes, and derivatives thereof.

15. The process of claim 1, wherein the solvent is selected from the group consisting of dioxane, toluene, 1,2-dichloroethane, acetonitrile, dibutyl ether, diethyl ether, hexane, tetrahydrofuran, and mixtures thereof.

16. The process of claim 1, wherein at least one additive is present during the reaction and is selected from the group consisting of trialkylamines and iodide salts.

17. The process of claim 1, wherein at least one additive is present during the reaction and the at least one additive includes at least one of triethylamine or TMEDA.

18. The process of claim 1, wherein at least one additive is present during the reaction and the at least one additive includes at least one of LiI, NaI, KI, or ammonium iodide.

19. The process of claim 1, wherein M and X of the compound of formula (II) are Zn and Br or I, respectively, X of the compound of formula (III) is I, the catalyst is [(3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P].sub.2PdI.sub.2, the additive is triethylamine, and the solvent is dioxane.

20. The process of claim 1, wherein M and X of the compound of formula (II) are Mg and Br or I, respectively, X of the compound of formula (III) is Cl, the catalyst is [(3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P].sub.2PdI.sub.2, and the solvent is Et.sub.2O.

21. A compound of formula (I): ##STR00112## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each, independently, an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, or heteroaryl group, each of which is optionally substituted with one or more substituents; wherein R.sup.2, R.sup.3, and/or R.sup.4, when taken together, optionally define an optionally substituted ring system; and R.sup.2, R.sup.3, and/or R.sup.4 are optionally covalently linked to R.sup.1.

22. The compound of claim 21, wherein R.sup.1 is sterically hindered.

23. The compound of claim 21, wherein R.sup.1 is selected from the group consisting of secondary and tertiary alkyl groups, secondary and tertiary alkenyl groups, and secondary and tertiary alkynyl groups, each of which is optionally substituted.

24. The compound of claim 21, wherein one or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is substituted with a least one silyl group.

25. The compound of claim 21, wherein the compound is selected from the group consisting of compounds of formulae (2), (3), (7)-(9), (13), (16)-(23), (25)-(27), and (30)-(47): ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117##

26. A composition comprising at least one compound of claim 21.

27. The composition of claim 26, wherein the composition is selected from the group consisting of aerospace materials, pharmaceuticals, agrochemicals, rubber materials, lubricants, hydraulic fluids, damping fluids, diffusion pump fluids, cryogenic fluids, waterproofing agents, hydrophobing agents, heat transfer media, anti-stick coatings, and fuel additives.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0024] In one aspect of the present invention, the present disclosure provides for a process for preparing a compound of formula (I):

##STR00011##

[0025] The process comprises the step of reacting a compound of formula (II):

R.sup.1-MX(II)

with a compound of formula (III):

##STR00012##

[0026] In the compounds of formula (II), M is Zn or Mg and R.sup.1 is an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, or heteroaryl group, each of which is optionally substituted with one or more substituents. At least one of these one or more substituents may optionally be a moiety of formula -MX, wherein M is Zn or Mg and X is Cl, Br, or I. Variable X of the compounds of formula (II) is Cl, Br, or I, or, when R.sup.1 is an alkyl group, X is optionally an alkyl group identical to that of R.sup.1. In certain embodiments, R.sup.1 is a sterically hindered group, such as a primary, secondary, or tertiary alkyl, alkenyl, or alkynyl group, each of which is optionally substituted.

[0027] In the compounds of formula (III), X is Cl, Br, I, OS(O).sub.2alkyl, OS(O).sub.2perfluoroalkyl, or OS(O).sub.2aryl. Examples of OS(O).sub.2alkyl, OS(O).sub.2perfluoroalkyl, and OS(O).sub.2aryl groups include, but are not limited to, methanesulfonate, trifluoromethanesulfonate, and toluenesulfonate groups, respectively. R.sup.2, R.sup.3, and R.sup.4 of the compounds of formula (III) are, independently, selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl group is optionally substituted with one or more substituents, as well as from Cl, Br, I, OS(O).sub.2alkyl, OS(O).sub.2perfluoroalkyl, and OS(O).sub.2aryl groups. In certain embodiments, R.sup.2, R.sup.3, and/or R.sup.4, when taken together, optionally define an optionally substituted ring system. Furthermore, R.sup.2, R.sup.3, and/or R.sup.4 are optionally covalently linked to R.sup.1 of the compound of formula (II).

[0028] In certain embodiments, at least one of the one or more optional substituents on R.sup.2, R.sup.3, and R.sup.4 of the compounds of formula (III) may be a moiety of formula SiR.sup.5R.sup.6X. R.sup.5 and R.sup.6 are each, independently, selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, heteroaryl, each of which, in turn, is optionally substituted with one or more substituents. X is Cl, Br, I, OS(O).sub.2alkyl, OS(O).sub.2perfluoroalkyl, or OS(O).sub.2aryl.

[0029] In certain embodiments, in addition to X, R.sup.2 and/or R.sup.3 and/or R.sup.4 of the compound of formula (III) is selected from the group consisting of Cl, Br, I, OS(O).sub.2alkyl groups, OS(O).sub.2perfluoroalkyl groups, and OS(O).sub.2aryl groups. Examples of such compounds of formula (III) include, but are not limited to, dimethyldichlorosilane (i.e, Me.sub.2SiCl.sub.2) and trichlorophenylsilane (i.e., PhSiCl.sub.3). These polychlorosilanes can be monoalkylated with alkyl zinc halides, as shown in the following reaction schemes:

##STR00013##

The respective ethoxy-substituted products result from post-reaction workup with ethanol to yield a stable adduct.

[0030] The compounds of formula (II) and (III) are reacted in the presence of a catalyst comprising a Group 8, 9, or 10 transition metal, a ligand, a solvent, and, optionally, an additive.

[0031] Any suitable catalyst comprising a Group 8, 9, or 10 transition metal (e.g., Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt) may be used in the processes of the present invention. In certain embodiments, the catalyst comprises a Group 8, 9, or 10 transition metal selected from the group consisting of Pd, Ni, Co, Rh, and Ir. In embodiments where the catalyst comprises Pd, examples of such catalysts include, but are not limited to, Pd(OAc).sub.2, PdBr.sub.2, PdI.sub.2, Pd(dba).sub.2, Pd(dba).sub.3, [allylPdCl].sub.2, Pd.sub.2dba.sub.3*CHCl.sub.3, [(3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P].sub.2PdI.sub.2, [(3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P].sub.2PdCl.sub.2, (COD)Pd(CH.sub.2TMS).sub.2, (COD)PdCl.sub.2, (PPh.sub.3).sub.2PdCl.sub.2, (PPh.sub.3).sub.4Pd, and (MeCN).sub.2PdCl.sub.2. In embodiments, where the catalyst comprises Ni, examples of such catalysts include, but are not limited to, Ni halide salts, Ni solvent complexes, and Ni(COD).sub.2.

[0032] Any suitable ligand may be used in the processes of the present invention. Examples of classes of such ligands include, but are not limited to, phosphine ligands, arsine ligands, nitrogen-containing ligands, and N-heterocyclic carbene (NHC) ligands. An example of an NHC ligand that may be used in the processes of the present invention includes, but is not limited to, a ligand having the following structure:

##STR00014##

For example, this particular ligand can be used to alkylate Me.sub.2PhSiCl with cyclohexylmagnesium bromide, as shown in the following reaction scheme:

##STR00015##

[0033] Examples of other particular ligands that may be used, include, but are not limited to, PPh.sub.3, (3,5-t-BuC.sub.6H.sub.3).sub.2P(tBu), Ph.sub.2P(tBu), PhP(t-Bu).sub.2, (3,5-C.sub.6H.sub.3(t-Bu).sub.2).sub.3P, (4-MeOC.sub.6H.sub.4).sub.3P, (t-Bu).sub.3P, (t-Bu).sub.2PCy, (t-Bu)PCy.sub.2, Cpy.sub.3P, Cy.sub.2PMe, Cy.sub.2PEt, Cy.sub.3P, (o-tol).sub.3P, (furyl).sub.3P, (4-FC.sub.6H.sub.4).sub.3P, (4-CF.sub.3C.sub.6H.sub.4).sub.3P, BIPHEP, NapthPhos, XantPhos, dppf, dppe, dppb, dpppe, dcpe, dcpp, dcpb, SPhos, XPhos, DavePhos, JohnPhos, BrettPhos, QPhos, AmgenPhos, RockPhos, RuPhos, VPhos, tBuXPhos, tBuBrettPhos, TrixiePhos, AZPhos, CPhos, (3,5-t-BuC.sub.6H.sub.3).sub.2P(iPr), (3,5-t-BuC.sub.6H.sub.3).sub.2P(Et), (3,5-t-BuC.sub.6H.sub.3).sub.2P(Me), (3,5-i-PrC.sub.6H.sub.3).sub.2P(tBu), (3,5-i-PrC.sub.6H.sub.3).sub.2P(iPr), (3,5-i-PrC.sub.6H.sub.3).sub.2P(Et), (3,5-i-PrC.sub.6H.sub.3).sub.2P(Me), (3,5-t-Bu-4-MeOC.sub.6H.sub.2).sub.2P(tBu), (3,5-t-Bu-4-MeOC.sub.6H.sub.2).sub.3P, BINAP, SIPr, IPr, IMes, ISMes, and derivatives thereof. In certain embodiments, the ligand can be a XantPhos derivative having the following structure:

##STR00016##

[0034] Any suitable solvent may be used in the processes of the present invention. Examples of such solvents include, but are not limited to, dioxane, toluene, 1,2-dichloroethane, acetonitrile, dibutyl ether, diethyl ether, hexane, tetrahydrofuran, and mixtures thereof.

[0035] Additives that facilitate the processes of the present invention may be present during the reaction. Examples of such additives include, but are not limited to, trialkylamines, such as triethylamine, TMEDA, and iodide salts, such as LiI, NaI, KI, or ammonium iodide salts.

[0036] The processes according the present invention can be performed at any suitable temperature. Examples of suitable temperatures include, but are not limited to, temperatures in the range of from 78 C. to 100 C. In certain embodiments, the reaction temperature is room or ambient temperature, i.e., approximately 20 to 25 C. In certain other embodiments, the reaction temperature is 50 C.

[0037] In another aspect of the present invention, the present disclosure provides for compounds of formula (I):

##STR00017##

wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined above. Substituents R.sup.2, R.sup.3, and/or R.sup.4, when taken together, optionally define an optionally substituted ring system and are optionally covalently linked to R.sup.1. In certain embodiments, R.sup.1 is a sterically hindered group, such as an optionally substituted secondary and tertiary alkyl, alkenyl, or alkynyl group. In certain embodiments, one or more of groups R, R.sup.2, R.sup.3, and R.sup.4 is substituted with a least one silyl group.

[0038] In another aspect of the present invention, the present disclosure provides for compositions and articles comprising at least one compound of formula (I). Examples of such compositions and articles include, but are not limited to, aerospace materials, pharmaceuticals, agrochemicals, rubber materials, lubricants, hydraulic fluids, damping fluids, diffusion pump fluids, cryogenic fluids, waterproofing agents, hydrophobing agents, heat transfer media, anti-stick coatings and fuel additives.

[0039] The following examples are included to demonstrate preferred embodiments. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the products, compositions, and methods described herein, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the disclosure.

EXAMPLES

[0040] General Experimental Details

[0041] Dioxane, trimethylamine, toluene, dibutyl ether (Bu.sub.2O), diethyl ether (Et.sub.2O), methyl tert-butyl ether (MTBE), triethylamine, dichloromethane (DCM), acetonitrile (MeCN), and tetrahydrofuran (THF), were dried on alumina according to published procedures. Cyclopentylmethyl ether (CPME) was dried over CaH.sub.2, distilled under N.sub.2, and stored in a Straus flask.

[0042] The following Grignard reagents were purchased from commercial suppliers and titrated with iodine before use: phenylmagnesium bromide [3M] in Et.sub.2O (Aldrich), ortho-tolylmagnesium bromide [2M] in Et.sub.2O (Aldrich), 2-mesitylmagnesium bromide [1M] in Et.sub.2O (Aldrich), cyclopentylmagnesium bromide [2M] in Et.sub.2O (Acros), and 2-methyl-2-phenylpropylmagnesium chloride [0.5M] in Et.sub.2O (Acros).

[0043] Instrumentation and Chromatography

[0044] 400 MHz .sup.1H, 101 MHz .sup.13C, and 376 MHz .sup.19F spectra were obtained on a 400 MHz FT-NMR spectrometer equipped with a Bruker CryoPlatform. 600 MHz .sup.1H, 151 MHz .sup.13C, 119 MHz .sup.29Si, and 243 MHz .sup.31P spectra were obtained on a 600 MHz FT-NMR spectrometer equipped with a Bruker SMART probe. All samples were analyzed in the indicated deutero-solvent and were recorded at ambient temperatures. All chemical shifts are reported in ppm. .sup.1H NMR spectra were calibrated using the residual protio-signal in deutero-solvents as a standard. .sup.13C NMR spectra were calibrated using the deutero-solvent as a standard. Product .sup.29Si spectra were calibrated using a hexamethyldisiloxane capillary standard at 7.32 ppm. IR spectra were recorded on a Nicolet Magma-IR 560 FT-IR spectrometer as thin films on KBr plates. High resolution MS data was obtained on a Waters GCT Premier spectrometer using chemical ionization (CI), electron ionization (EI), or liquid injection field desorption ionization (LIFDI). Vacuum controller refers to J-Kem Digital Vacuum Regulator Model 200. Unless otherwise noted, column chromatography was performed either by hand or by use of Isolera 4 Biotage unit with 40-63 m silica gel, and the eluent reported in parentheses. Analytical thin-layer chromatography (TLC) was performed on silica gel (60 F.sub.254 Merck) pre-coated glass plates and visualized by UV or by staining with iodine, KMnO.sub.4, or ceric ammonium molybdate (CAM).

Synthesis of Ligand DrewPhos

[0045] ##STR00018##

[0046] An oven-dried 500 mL round bottom flask equipped with a magnetic stir bar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the rubber septum was removed, 1-bromo-3,5-di-tert-butylbenzene (32.4 g, 120 mmol, 3.01 equiv.) was added, and the septum replaced. The flask was then purged with N.sub.2 for 15 minutes. THF (240 mL, [0.5 M]) was added and the flask was cool to 78 C. in a dry ice/acetone bath. While stirring, nBuLi (48.2 mL, 120 mmol, 3 equiv., [2.49 M] in hexanes) was added dropwise via syringe pump over 30 minutes. PCl.sub.3 (3.5 mL, 40 mmol, 1 equiv.) was added dropwise via syringe pump over 15 minutes. After the addition was complete, the flask was warmed to 0 C. in an ice/water bath and stirred for 4 hours. The flask was allowed to warm to RT, the septum was removed and the reaction was quenched by adding brine (100 mL). The reaction was poured into a separatory funnel and the product was extracted 2 with Et.sub.2O (100 mL). The organic layer was dried over MgSO.sub.4, filtered through a glass frit, and the solvent removed in vacuo. The product was purified by recrystallization from hot EtOH (200 mL), cooled under ambient conditions, then placed in a 20 C. freezer overnight. Collection of the solid via filtration and washing with EtOH resulted in white crystals (10.6 g, 44% yield): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.38 (t, J=1.8 Hz, 3H), 7.12 (dd, J=8.5, 1.8 Hz, 6H), 1.22 (s, 54H); .sup.13C NMR (151 MHz, CDCl.sub.3) 150.6 (d, J=6.7 Hz), 137.3 (d, J=9.4 Hz), 128.1 (d, J=19.3 Hz), 122.4, 35.0, 31.5; .sup.31P NMR (243 MHz, CDCl.sub.3) 3.59; FTIR (cm.sup.1): 2963, 1589, 1577, 1362, 1249, 1130, 875, 710; mp=145-147 C.; HRMS (LIFDI) m/z, calculated for [C.sub.42H.sub.63P].sup.+: 598.4667; found: 598.4688.

Synthesis of Catalyst (DrewPhos).SUB.2.PdI.SUB.2

[0047] ##STR00019##

[0048] A 50 mL round bottom flask equipped with a magnetic stirbar was charged with palladium(II) iodide (1.08 g, 3 mmol, 1.0 equiv.) and DrewPhos (3.59 g, 6 mmol, 2.0 equiv.). The flask was sealed with a rubber septum and purged 10 min with N.sub.2. Toluene (24 mL) was added via syringe and the reaction was stirred for 24 hours at 85 C. The reaction was cooled to RT, transferred to a 250 mL round bottom flask and the solvent evaporated in vacuo. The resulting solid was recrystallized from hot 3:1 ethanol:toluene (100 mL), cooled under ambient conditions, then placed in a 20 C.freezer overnight. Collection of the solid via filtration resulted in a stable, red solid (3.52 g, 75% yield). A second crop of product was obtained by subsequent recrystallization with same solvent system resulted in red crystals (900 mg, 19%). Total 4.42 g, 95%: .sup.1H NMR (600 MHz, CDCl.sub.3) 7.60-7.54 (m, 12H), 7.29 (s, 6H), 1.21 (s, 108H); .sup.13C NMR (151 MHz, CDCl.sub.3) 149.2 (t, J=5.1 Hz), 134.5 (t, J=24.9 Hz), 129.9 (t, J=6.2 Hz), 123.2, 35.1, 31.6; .sup.31P NMR (243 MHz, CDCl.sub.3) 18.90; FTIR (cm.sup.1): 2953, 1589, 1384, 1247, 1087, 702, 584; mp=>250 C. HRMS (LIFDI) m/z, calculated for [C.sub.84H.sub.126P.sub.2PdI].sup.+:1429.7414; found: 1429.7373.

Synthesis of Alkyl Zinc Halides

[0049] General Procedure

[0050] An oven dried Schlenk flask equipped with a magnetic stirbar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the septum removed, and zinc dust (2 equiv.) added. The septum was replaced; the flask was attached to a double manifold and evacuated. Under vacuum, the zinc was heated for 5 minutes with a heat gun then allowed to cool to RT under vacuum. The flask was backfilled with N.sub.2 then dioxane [2 M], trimethylsilyl chloride (0.03 equiv), and alkyl bromide (1 equiv) were added. The flask was then stirred in an oil bath at 100 C. for the indicated time. Conversion of starting halide was monitored via GC by quenching reaction aliquots with saturated NH.sub.4Cl solution and extracting with Et.sub.2O. Once all starting halide was consumed, the excess zinc was allowed to settle while the flask cooled. The mixture was filtered via cannula to a Schlenk tube. If insoluble particles persist, filtration through a 0.2 m PTFE syringe filter was employed. Solutions were then titrated according to the literature procedure by Knochel.

Synthesis of Cyclohexylzinc Iodide

[0051] ##STR00020##

[0052] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (3.92 g, 60 mmol), dioxane (15 mL), trimethylsilyl chloride (115 L, 98 mg, 0.9 mmol), and cyclohexyl iodide (3.88 mL, 6.3 g, 30 mmol). The flask was heated to 100 C. for 12 hours. Filtration and titration resulted in a [0.97 M] solution of cyclohexylzinc iodide in dioxane.

Synthesis of Isopropylzinc Iodide

[0053] ##STR00021##

[0054] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (3.92 g, 60 mmol), dioxane (15 mL), trimethylsilyl chloride (115 L, 98 mg, 0.9 mmol), and isopropyl iodide (3.0 mL, 5.1 g, 30 mmol). The flask was heated to 100 C. for 20 hours. Filtration and titration resulted in a [1.56 M] solution of isopropylzinc iodide in dioxane.

Synthesis of Isopropylzinc Bromide

[0055] ##STR00022##

[0056] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (3.92 g, 60 mmol), dioxane (15 mL), trimethylsilyl chloride (120 L, 102 mg, 0.9 mmol), and isopropyl bromide (2.9 mL, 3.8 g, 31 mmol). The flask was heated to 100 C. for 20 hours. Filtration and titration resulted in a [1.81 M] solution of isopropylzinc bromide.

Synthesis of Isobutylzinc Iodide

[0057] ##STR00023##

[0058] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (3.92 g, 60 mmol), dioxane (15 mL), trimethylsilyl chloride (115 L, 98 mg, 0.9 mmol), and isobutyl iodide (3.6 mL, 5.8 g, 30 mmol). The flask was heated to 100 C. for 17 hours. Filtration and titration resulted in a [1.59 M] solution of isobutylzinc iodide in dioxane.

Synthesis of Isobutylzinc Bromide

[0059] ##STR00024##

[0060] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (3.92 g, 60 mmol), dioxane (15 mL), trimethylsilyl chloride (115 L, 98 mg, 0.9 mmol), and isobutyl bromide (3.3 mL, 4.2 g, 30 mmol). The flask was heated to 100 C. for 17 hours. Filtration and titration resulted in a [1.40 M] solution of isobutylzinc bromide in dioxane.

Synthesis of n-Propylzinc Iodide

[0061] ##STR00025##

[0062] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (1.52 g, 23 mmol), dioxane (6 mL), trimethylsilyl chloride (50 L, 45 mg, 0.4 mmol), and n-propyl iodide (1.5 mL, 2.61 g, 15 mmol). The flask was heated to 100 C. for 20 hours. Filtration and titration resulted in a [2.25 M] solution of n-propylzinc iodide in dioxane.

Synthesis of Cyclopentylzinc Bromide

[0063] ##STR00026##

[0064] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (2.6 g, 40 mmol), dioxane (10 mL), trimethylsilyl chloride (80 L, 66 mg 0.6 mmol), and cyclopentyl bromide (2.2 mL, 20 mmol). The flask was heated to 100 C. for 18 hours. Filtration and titration resulted in a [0.89 M] solution of cyclopentylzinc bromide.

Synthesis of n-Butylzinc Bromide

[0065] ##STR00027##

[0066] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (3.92 g, 60 mmol), dioxane (15 mL), trimethylsilyl chloride (115 L, 98 mg, 0.9 mmol), and n-butyl bromide (3.3 mL, 4.2 g, 30 mmol). The flask was heated to 100 C. for 17 hours. Filtration and titration resulted in a [1.51 M] solution of n-butylzinc bromide in dioxane.

Synthesis of Pentan-3-ylzinc Bromide

[0067] ##STR00028##

[0068] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (2.6 g, 40 mmol), dioxane (10 mL), trimethylsilyl chloride (80 L, 66 mg 60 mol), and 3-bromopentane (2.5 mL, 3.0 g, 20 mmol). The flask was heated to 100 C. for 4 hours. Filtration and titration resulted in a [1.35 M] solution of pentan-3-ylzinc bromide.

Synthesis of 1-Octylethylzinc Bromide

[0069] ##STR00029##

[0070] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (2.1 g, 32 mmol), dioxane (8 mL), trimethylsilyl chloride (60 L, 52 mg, 0.5 mmol), and 2-bromodecane (3.4 mL, 16 mmol). The flask was heated to 100 C. for 2 hours. Filtration and titration resulted in a [1.00 M] solution of 1-octylethylzinc bromide.

Synthesis of (4-Methylpentan-2-yl)zinc Bromide

[0071] ##STR00030##

[0072] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (1.83 g, 28 mmol), dioxane (7 mL), trimethylsilyl chloride (50 L, 43 mg, 0.4 mmol), and 2-bromo-4-methylpentane (2.29 g, 14 mmol). The flask was heated to 100 C. for 2 hours. Filtration and titration resulted in a [0.91 M] solution of (4-methylpentan-2-yl)zinc bromide in dioxane.

Synthesis of (1S,4R)-Bicyclo[2.2.2.1]heptan-2-ylzinc Bromide

[0073] ##STR00031##

[0074] According to the general procedure, a 25 mL Schlenk flask was charged with zinc dust (2.6 g, 40 mmol), dioxane (10 mL), trimethylsilyl chloride (80 L, 65 mg, 0.6 mmol), and 2-exo-bromonorbornane (2.6 mL, 3.5 g, 20 mmol). The flask was heated to 100 C. for 3 hours. Filtration and titration resulted in a [1.23 M] solution of (1S,4R)-bicyclo[2.2.1]heptan-2-ylzinc bromide.

Synthesis of -Methylbenzylzinc Bromide

[0075] ##STR00032##

[0076] A 50 mL Schlenk flask equipped with a stirbar and rubber septum attached to a double manifold (with cold trap) was charged with titrated, [0.38 M] -methylbenzylzinc bromide (Aldrich) in THF (25 mL, 9.5 mmol) and dioxane (8 mL). Solvent was removed in vacuo (26 C./0.3 mm Hg) until total volume was reduced to approximately 2-3 mL (solution became viscous). Dioxane (12 mL) was added and solvents were removed again in vacuo (26 C./0.2 mm Hg) until total volume was reduced to approximately 2-3 mL (viscous solution). Dioxane (8 mL) was added to afford a total volume of approximately 10 mL. Filtration via cannula to a Schlenk bomb and titration resulted in a [0.82 M] solution of -methylbenzylzinc bromide in dioxane. The solvent exchange setup diagram is depicted in FIG. 2.

Synthesis of (4-Phenylbutan-2-yl)zinc Bromide

[0077] ##STR00033##

[0078] According to the general procedure, a 10 mL Schlenk flask was charged with zinc dust (1.3 g, 20 mmol), dioxane (5 mL), trimethylsilyl chloride (40 L, 33 mg 0.3 mmol), and 2-bromo-4-phenylbutane (2.1 g, 10 mmol). The flask was heated to 100 C. for 2 hours. Filtration and titration resulted in a [1.32 M] solution of (4-phenylbutan-2-yl)zinc bromide.

Synthesis of (4-(4-(Ethoxycarbonyl)phenyl)butan-2yl)zinc Bromide

[0079] ##STR00034##

[0080] According to the general procedure, a 10 mL Schlenk flask was charged with zinc dust (1.3 g, 20 mmol), dioxane (6 mL), trimethylsilyl chloride (100 L, 86 mg, 0.8 mmol), and ethyl 4-(3-bromobutyl)benzoate (2.85 g, 10 mmol). The flask was heated to 100 C. for 2 hours. Filtration and titration resulted in a [1.09 M] solution of (4-(4-(ethoxycarbonyl)phenyl)butan-2yl)zinc bromide in dioxane.

Synthesis of (4-(4-Methoxyphenyl)butan-2yl)zinc Bromide

[0081] ##STR00035##

[0082] According to the general procedure, a 10 mL Schlenk flask was charged with zinc dust (1.3 g, 20 mmol), dioxane (5 mL), trimethylsilyl chloride (40 L, 33 mg, 0.3 mmol), and 1-(3-bromobutyl)-4-methoxybenzene (2.4 g, 10 mmol). The flask was heated to 100 C. for 2 hours. Filtration and titration resulted in a [1.26 M] solution of (4-(4-methoxyphenyl)butan-2yl)zinc bromide.

Synthesis of (4-(4-Chlorophenyl)butan-2-yl)zinc Bromide

[0083] ##STR00036##

[0084] According to the general procedure, a 10 mL Schlenk flask was charged with zinc dust (1.3 g, 20 mmol), dioxane (5 mL), trimethylsilyl chloride (40 L, 33 mg, 0.3 mmol), and 1-(3-bromobutyl)-4-chlorobenzene (2.5 g, 10 mmol). The flask was heated to 100 C. for 2 hours. Filtration and titration resulted in a [1.25 M] solution of (4-(4-chlorophenyl)butan-2-yl)zinc bromide.

Synthesis of (4-(4-(Trifluoromethyl)phenyl)butan-2yl)zinc Bromide

[0085] ##STR00037##

[0086] According to the general procedure, a 10 mL Schlenk flask was charged with zinc dust (1.3 g, 20 mmol), dioxane (5 mL), trimethylsilyl chloride (40 L, 33 mg, 0.3 mmol), and 1-(3-bromobutyl)-4-(trifluoromethyl)benzene (2.82 g, 10 mmol). The flask was heated to 100 C. for 2 hours. Filtration and titration resulted in a [1.14 M] solution of (4-(4-(trifluoromethyl)phenyl)butan-2yl)zinc bromide in dioxane.

Synthesis of (3-Methylbutan-2-yl)zinc Iodide

[0087] ##STR00038##

[0088] According to a modified procedure, a 10 mL Schlenk flask was charged with zinc dust (294 mg, 4.5 mmol), dioxane (1 mL), trimethylsilyl chloride (20 L, 17 mg, 0.1 mmol), and 2-iodo-3-methylbutane (446 mg, 2.3 mmol) was added dissolved in dry dioxane (1.1 mL). The flask was heated to 50 C. for 1 hour. Filtration and titration resulted in a [1.05 M] solution of (3-methylbutan-2-yl)zinc iodide.

Synthesis of (3,3-Dimethylbutan-2-yl)zinc Iodide

[0089] ##STR00039##

[0090] According to a modified procedure, a 10 mL Schlenk flask was charged with zinc dust (0.8 g, 12 mmol), dioxane (5 mL), trimethylsilyl chloride (50 L, 43 mg, 0.4 mmol), and 3-iodo-2,2-dimethylbutane (1.31 g, 6 mmol). The flask was heated to 50 C. for 2 hours. Filtration and titration resulted in a [0.54 M] solution of (3,3-dimethylbutan-2-yl)zinc iodide in dioxane.

Synthesis of Alkylmagnesium Halides

[0091] General Procedure

[0092] An oven dried round bottom flask equipped with a magnetic stirbar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the septum removed, magnesium turnings (1.5 equiv.) and a single chip of I.sub.2 (20-30 mg) were added. The septum was replaced; the flask was attached to a double manifold and purged with N.sub.2 for 10 min. The flask was held under positive N.sub.2 then Et.sub.2O [3 M] was added. The solution was stirred until clarity was reached (disappearance of brown I.sub.2 color). An initial amount of alkyl halide (200-400 L) was added to start the reaction as evidenced by a minor exotherm. If reaction does not initiate, gentle warming (for example with a heating mantle) may be necessary. Once initiated, the alkyl halide was added dropwise so as to keep the mixture warm, but below full reflux. If desired, a reflux condenser may be used as well. After full addition of the alkyl halide, the flask was allowed to stir at RT for an additional 1-4 hours. The excess magnesium was allowed to settle and the mixture was filtered via cannula to a Schlenk tube. If insoluble particles persist, filtration through a 0.2 m PTFE syringe filter was employed. Solutions were then titrated according to the literature procedure by Knochel. Titration concentrations used in the isolation runs in Section 5 may differ from those reported here. The procedures listed below reflect titrations from specific experimental runs.

Synthesis of Isopropylmagnesium Iodide

[0093] ##STR00040##

[0094] According to the general procedure, magnesium turnings (1.1 mg, 45 mmol, 1.5 equiv.), diethyl ether (10 mL), I.sub.2 chip, and isopropyl iodide (3.0 mL, 5.1 g, 30 mmol, 1 equiv.) were combined under nitrogen and stirred for 2 hours at RT. Filtration and titration resulted in a [1.84 M] solution of isopropylmagnesium iodide.

Synthesis of Isopropylmagnesium Bromide

[0095] ##STR00041##

[0096] According to the general procedure, magnesium turnings (1.1 mg, 45 mmol, 1.5 equiv.), diethyl ether (10 mL), I.sub.2 chip, and isopropyl bromide (2.8 mL, 3.69 g, 30 mmol, 1 equiv.) were combined under nitrogen and stirred for 2 hours at RT. Filtration and titration resulted in a [2.23 M] solution of isopropylmagnesium bromide.

Synthesis of Isopropylmagnesium Chloride

[0097] ##STR00042##

[0098] According to the general procedure, magnesium turnings (1.1 mg, 45 mmol, 1.5 equiv.), diethyl ether (10 mL), no iodine, and isopropyl chloride (2.7 mL, 2.36 g, 30 mmol) were combined under nitrogen and stirred for 4 hours at RT. Filtration and titration resulted in a [2.65 M] solution of isopropylmagnesium chloride.

Synthesis of n-Butylmagnesium Bromide

[0099] ##STR00043##

[0100] According to the general procedure, magnesium turnings (730 mg, 30 mmol), diethyl ether (7 mL), no iodine, and a solution of n-butyl bromide (2.7 mL, 3.4 g, 25 mmol) in diethyl ether (5 mL) were combined under nitrogen and stirred for 4 hours at RT. Filtration and titration resulted in a [1.93 M] solution of n-butylmagnesium bromide.

Synthesis of 3-Pentyl magnesium Bromide

[0101] ##STR00044##

[0102] According to the general procedure, magnesium turnings (300 mg, 12 mmol), diethyl ether (3 mL), I.sub.2 chip, and solution of 3-bromopentane (1.2 mL, 1.5 g, 10 mmol) in diethyl ether (2 mL) were combined under nitrogen and stirred for 4 hours at RT. Filtration and titration resulted in a [0.67 M] solution of 3-pentylmagnesium bromide.

Synthesis of (1S,4R)-Bicyclo[2.2.1]heptan-2-ylmagnesium Bromide

[0103] ##STR00045##

[0104] According to the general procedure, magnesium turnings (730 mg, 30 mmol, 1.5 equiv.), diethyl ether (6.7 mL), I.sub.2 chip, and (1S,4R)-2-bromobicyclo[2.2.1]heptane (2.6 mL, 3.5 g, 20 mmol, 1 equiv.) were combined under nitrogen and stirred 3 hour at RT. Filtration and titration resulted in a [1.21 M] solution of (1S,4R)-bicyclo[2.2.1]heptan-2-ylmagnesium bromide in an exo:endo ratio of 41:59, as determined by NMR.

Synthesis of Neopentylmagnesium Bromide

[0105] ##STR00046##

[0106] According to the general procedure, magnesium turnings (730 mg, 30 mmol), diethyl ether (7 mL), I.sub.2 chip, and solution of neopentyl bromide (3 mL, 3.6 g, 24 mmol) in diethyl ether (5 mL). Filtration and titration resulted in a [0.95 M] solution of neopentylmagnesium bromide.

Synthesis of (4-Phenylbutan-2-yl)magnesium Bromide

[0107] ##STR00047##

[0108] According to the general procedure, magnesium turnings (1.1 g, 45 mmol, 1.5 equiv.), I.sub.2 chip, Et.sub.2O (10 mL), and (3-bromobutyl)benzene (6.4 g, 30 mmol, 1 equiv.) were combined under nitrogen and stirred for 1 hour at RT. Filtration and iodometric titration resulted in a [1.34 M] solution of (4-phenylbutan-2-yl)magnesium bromide.

Synthesis of (4-(4-Chlorophenyl)butan-2-yl)magnesium Bromide (GR9)

[0109] ##STR00048##

[0110] According to the general procedure, magnesium turnings (292 mg, 12 mmol, 1.2 equiv.), I.sub.2 chip, Et.sub.2O (3.3 mL), and 1-(3-bromobutyl)-4-chlorobenzene (2.48 g, 10 mmol, 1 equiv.) were combined under nitrogen and stirred for 2 hours at RT. Filtration and iodometric titration resulted in a [0.85 M] solution of (4-(4-chlorophenyl)butan-2-yl)magnesium bromide.

Synthesis of (4-(4-Methoxyphenyl)butan-2-yl)magnesium Bromide

[0111] ##STR00049##

[0112] According to the general procedure, magnesium turnings (292 mg, 12 mmol, 1.2 equiv.), I.sub.2 chip, Et.sub.2O (3.3 mL), and 1-(3-bromobutyl)-4-methoxybenzene (2.43 g, 10 mmol, 1 equiv.) were combined under nitrogen and stirred for 2 hours at RT. Filtration and iodometric titration resulted in a [0.85 M] solution of (4-(4-methoxyphenyl)butan-2-yl)magnesium bromide.

Synthesis of (1-Phenylethyl)magnesium Bromide)

[0113] ##STR00050##

[0114] According to a modified version of the general procedure, magnesium turnings (1.1 g, 45 mmol, 1.5 equiv.), diethyl ether (10 mL), and I.sub.2 chip were added. Once clarity of the solution was reached, the flask was cooled to 0 C. in an ice/water bath. Stirring at 0 C., (1-bromoethyl)benzene (5.6 g, 4.1 mL, 30 mmol, 1 equiv.) was added dropwise via syringe pump over 1 hour. After addition, the flask was allowed to stir at RT 3 h. Filtration and titration resulted in a [0.55 M] solution of (1-phenylethyl)magnesium bromide.

Synthesis of Silahydrocarbons

[0115] General Procedure A

[0116] Reactions were run at [0.5 M] overall concentration based on the sum of all liquid reagents. THF quenches were performed for certain substrates due to inseparable disiloxane formed upon aqueous workup. This quench generates the more easily separated (4-iodobutoxy)silane through silyl iodide induced ring opening of THF.

[0117] An oven dried 10 mL Schlenk flask equipped with a magnetic stirbar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the rubber septum was removed, and (DrewPhos).sub.2PdI.sub.2 (0.01 equiv.) was added. The septum was replaced and the flask purged with N.sub.2 for 10 minutes. Dioxane, triethylamine (1 equiv.), silyl iodide (2 equiv.), and alkylzinc bromide (1 equiv.) were added via syringe. The flask was then stirred at RT for the indicated time. The reaction was quenched as indicated, diluted with Et.sub.2O (20 mL) or EtOAc (20 mL) then washed 2 times with brine (20 mL). The organic layer was dried over MgSO.sub.4, filtered, and the solvent removed in vacuo. The crude material was purified via silica gel flash chromatography in the indicated solvent.

[0118] General Procedure B: Room Temperature Coupling

[0119] An oven dried 10 mL Schlenk flask equipped with a magnetic stirbar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the rubber septum was removed, and (DrewPhos).sub.2PdI.sub.2 (0.01 equiv.) was added. The septum was replaced and the flask purged with N.sub.2 for 10 minutes.

[0120] Et.sub.2O, silyl chloride (1.2 equiv.), and alkylmagnesium halide (1 equiv.) were added sequentially via syringe. The solution was then stirred at RT for 24 h. A vent needle was added and the reaction was quenched with EtOAc (3 mL) then H.sub.2O (3 mL) via syringe. The mixture was washed 2 times with brine (20 mL) and extracted using EtOAc or Et.sub.2O. The combined organic layer was dried over MgSO.sub.4, filtered, and the solvent removed in vacuo. The crude material was purified via silica gel flash chromatography in the indicated solvent.

[0121] General Procedure C: 50 C. Coupling

[0122] An oven dried 10 mL Schlenk flask equipped with a magnetic stirbar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the rubber septum was removed, and (DrewPhos).sub.2PdI.sub.2 (0.01 equiv.) was added. The septum was replaced and the flask purged with N.sub.2 for 10 minutes. Bu.sub.2O, silyl chloride (2 equiv.), and alkylmagnesium halide (1 equiv.) were added sequentially via syringe. The solution was then stirred in an oil bathour at 50 C. for 24 h. The flask was cooled to RT, a vent needle was added and the reaction was quenched with EtOAc (3 mL) then H.sub.2O (3 mL) via syringe. The mixture was washed 2 times with brine (20 mL) and extracted using EtOAc or Et.sub.2O. The combined organic layer was dried over MgSO.sub.4, filtered, and the solvent removed in vacuo. The crude material was purified via silica gel flash chromatography in the indicated solvent.

[0123] General Procedure D: Coupling Using Solid Silyl Chlorides

[0124] An oven dried 10 mL Schlenk flask equipped with a magnetic stirbar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the rubber septum was removed, (DrewPhos).sub.2PdI.sub.2 (0.01 equiv.) and silyl chloride (2 equiv.) were added. The septum was replaced and the flask purged with N.sub.2 for 10 minutes. Bu.sub.2O and alkylmagnesium halide (1 equiv.) were added sequentially via syringe. The solution was then stirred in an oil bathour at the indicated temperature for 24 h. The flask was cooled to RT, a vent needle was added and the reaction was quenched with EtOAc (3 mL) then H.sub.2O (3 mL) via syringe. The mixture was washed 2 times with brine (20 mL) and extracted using EtOAc or Et.sub.2O. The combined organic layer was dried over MgSO.sub.4, filtered, and the solvent removed in vacuo. The crude material was purified via silica gel flash chromatography in the indicated solvent.

Example 1Synthesis of Compound (1)

[0125] ##STR00051##

[0126] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (820 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.56 M] isopropylzinc iodide (640 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 1 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (1) as a clear volatile oil (165.1 mg, 93%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.59-7.45 (m, 2H), 7.44-7.31 (m, 3H), 1.02-0.92 (m, 7H), 0.25 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 138.7, 134.1, 128.9, 127.7, 17.7, 13.9, 5.2; .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.40; FTIR (cm.sup.1): 2955, 2864, 1463, 1427, 1248, 1112, 882, 831, 812, 770, 733, 699. HRMS (CI) m/z, calculated for [C.sub.11H.sub.18Si].sup.+: 178.1178; found: 178.1179.

[0127] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (940 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.79 M] isopropylzinc bromide (560 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (1) as a clear volatile oil (160.5 mg, 90%). NMR spectra matched previous isolation: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.57-7.45 (m, 2H), 7.40-7.32 (m, 3H), 1.07-0.86 (m, 7H), 0.25 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 138.7, 134.1, 128.9, 127.7, 17.7, 13.9, 5.2.

[0128] A two dram vial with stirbar (open to air) was charged with (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (910 L), triethylamine (140 L, 1 mmol) and dimethylphenylsilyl iodide (360 L, 2 mmol). The vial was sealed with a Teflon lined cap. While stirring, the cap was removed, [1.70 M] solution isopropylzinc iodide (590 L, 1 mmol) was added via syringe, and the cap was replaced. Stirring at RT was continued for 1 h. The reaction was quenched by removing the cap and adding wet EtOAc (0.5 mL) and brine (3 mL) via syringe and then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (1) as a clear volatile oil (156.1 mg, 88%). NMR spectra matched previous isolations: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52-7.49 (m, 2H), 7.36-7.35 (m, 3H), 0.99-0.94 (m, 7H), 0.25 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 138.6, 133.9, 128.7, 127.6, 17.6, 13.8, 5.3.

[0129] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (390 mg, 0.25 mmol), dioxane (21 mL), triethylamine (3.5 mL, 25 mmol), dimethylphenylsilyl iodide (9 mL, 50 mmol), and [1.52 M] isopropylzinc bromide (16.5 mL, 25 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with THF (10 mL), stirred for 15 min then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (1) as a clear volatile oil (4.35 g, 98%). NMR spectra matched previous isolation: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.53-7.49 (m, 2H), 7.37-7.33 (m, 3H), 0.97-0.94 (m, 7H), 0.25 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 138.8, 134.1, 128.9, 127.7, 17.7, 13.9, 5.2.

[0130] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.36 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [2.29 M]isopropylmagnesium bromide (440 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 1 h. After workup, the crude product was purified via silica gel flash chromatography (hexanes) to afford compound (1) as a clear oil (178 mg, 99%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.55-7.50 (m, 2H), 7.39-7.33 (m, 3H), 1.01-0.94 (m, 7H), 0.26 (s, 6H). .sup.13C NMR (151 MHz, CDCl.sub.3) 138.8, 134.1, 128.9, 127.8, 17.7, 13.9, 5.2. .sup.29Si NMR (119 MHz, CDCl.sub.3) 0.4.

Example 2Synthesis of Compound (2)

[0131] ##STR00052##

[0132] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (1.00 mL), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [2.25 M] n-propylzinc iodide (440 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 1 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (2) as a clear very volatile oil (169.5 mg, 96%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.56-7.49 (m, 2H), 7.39-7.31 (m, 3H), 1.42-1.31 (m, 2H), 0.96 (t, J=7.2 Hz, 3H), 0.79-0.72 (m, 2H), 0.26 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 139.9, 133.7, 128.9, 127.8, 18.51, 18.48, 17.6, 2.8; .sup.29Si NMR (119 MHz, CDCl.sub.3) -3.37; FTIR (cm.sup.1): 2955, 2868, 1427, 1248, 1114, 1065, 997, 882, 834, 767, 727, 699. HRMS (CI) m/z, calculated for [C.sub.10H.sub.15Si].sup.+: 163.0943; found: 163.0941.

Example 3Synthesis of Compound (3)

[0133] ##STR00053##

[0134] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (900 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.59 M] isobutylzinc iodide (640 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 1 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (3) as a clear volatile oil (187.0 mg, 95%). NMR spectra matched previous isolation: .sup.1H NMR (400 MHz, CDCl.sub.3) 7.58-7.44 (m, 2H), 7.43-7.31 (m, 3H), 1.77 (dh, J=13.3, 6.6 Hz, 1H), 0.90 (d, J=6.6 Hz, 6H), 0.77 (d, J=6.9 Hz, 2H), 0.29 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 140.4, 133.7, 128.8, 127.8, 26.50, 26.48, 25.1, 1.9.

[0135] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (800 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.34 M] isobutylzinc bromide (750 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound 3 as a clear volatile oil (183.3 mg, 95%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.55-7.50 (m, 2H), 7.38-7.32 (m, 3H), 1.77 (dh, J=13.3, 6.7 Hz, 1H), 0.91 (d, J=6.6 Hz, 6H), 0.78 (d, J=6.9 Hz, 2H), 0.29 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 140.3, 133.7, 128.8, 127.8, 26.50, 26.48, 25.1, 1.9; .sup.29Si NMR (119 MHz, CDCl.sub.3) -4.17; FTIR (cm.sup.1): 2953, 2893, 2361, 2338, 1248, 1112, 838, 812, 790, 698. HRMS (CI) m/z, calculated for [C.sub.12H.sub.19Si].sup.+: 191.1256; found: 191.1253.

Example 4Synthesis of Compound (4)

[0136] ##STR00054##

[0137] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (440 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [0.97 M] cyclohexylzinc iodide (1.00 mL, 0.97 mmol) were combined under N.sub.2 and stirred at RT for 1 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (4) as a clear oil (205.6 mg, 97%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.52-7.47 (m, 2H), 7.40-7.32 (m, 3H), 1.75-1.61 (m, 5H), 1.27-1.02 (m, 5H), 0.84-0.73 (m, 1H), 0.24 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 138.8, 134.1, 128.8, 127.7, 28.2, 27.5, 27.0, 25.9, 5.1; .sup.29Si NMR (119 MHz, CDCl.sub.3) -2.20; FTIR (cm.sup.1): 2919, 2846, 1446, 1427, 1247, 1112, 850, 834, 818, 770, 699. HRMS (CI) m/z, calculated for [C.sub.14H.sub.22Si].sup.+: 218.1491; found: 218.1486.

Example 5Synthesis of Compound (5)

[0138] ##STR00055##

[0139] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (900 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.60 M] n-butylzinc bromide (630 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (5) as a clear oil (175.1 mg, 91%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.55-7.49 (m, 2H), 7.39-7.33 (m, 3H), 1.37-1.26 (m, 4H), 0.87 (t, J=6.9 Hz, 3H), 0.80-0.73 (m, 2H), 0.26 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 139.9, 133.7, 128.9, 127.8, 26.7, 26.2, 15.6, 13.9, 2.9; .sup.29Si NMR (119 MHz, CDCl.sub.3) -3.08; FTIR (cm.sup.1): 2956, 2922, 2872, 1427, 1248, 1113, 887, 837, 779, 727, 699. HRMS (CI) m/z, calculated for [C.sub.1H.sub.17Si].sup.+: 177.1100; found: 177.1102.

[0140] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.32 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [2.1 M] n-butylmagnesium bromide (480 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 1 h. After workup, the crude product was purified via silica gel flash chromatography (hexanes) to afford compound (3) as a clear oil (192 mg, 99%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.55-7.48 (m, 2H), 7.39-7.32 (m, 3H), 1.37-1.26 (m, 4H), 0.87 (t, J=6.9 Hz, 3H), 0.78-0.73 (m, 2H), 0.26 (s, 6H). .sup.13C NMR (151 MHz, CDCl.sub.3) 139.9, 133.7, 128.9, 127.8, 26.7, 26.2, 15.6, 13.9, 2.9. .sup.29Si NMR (119 MHz, CDCl.sub.3) 3.1.

Example 6Synthesis of Compound (6)

[0141] ##STR00056##

[0142] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 16 mg, 10 mol), dioxane (380 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [0.89 M] cyclopentylzinc bromide (1.1 mL, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet Et.sub.2O (3 mL) and H.sub.2O (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (6) as a clear oil (197 mg, 97%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.55-7.50 (m, 2H), 7.36-7.33 (m, 3H), 1.80-1.73 (m, 2H), 1.59-1.46 (m, 4H), 1.36-1.25 (m, 2H), 1.11 (tt, J=8.4 Hz, 1H), 0.25 (s, 6H); .sup.13C NMR (151 MHz, CDCl.sub.3) 139.4, 133.9, 128.7, 127.6, 28.2, 27.0, 25.5, 4.5; .sup.29Si NMR (119 MHz, CDCl.sub.3) 2.01; FTIR (cm.sup.1): 3068, 2950, 2862, 1427, 1248, 1114, 827, 811, 699, 415. HRMS (CI) m/z, calculated for [C.sub.13H.sub.20Si].sup.+: 204.1334; found: 204.1337.

[0143] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), diethyl ether (1.24 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [1.77 M]cyclopentylmagnesium bromide (0.56 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (6) as a clear oil (200 mg, 99%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.56-7.52 (m, 2H), 7.40-7.32 (m, 3H), 1.83-1.72 (m, 2H), 1.58-1.49 (m, 4H), 1.39-1.27 (m, 2H), 1.13 (tt, J=10.8, 8.2 Hz, 1H), 0.26 (s, 6H). .sup.13C NMR (151 MHz, CDCl.sub.3) 139.5, 134.0, 128.8, 127.8, 28.4, 27.2, 25.6, 4.3. .sup.29Si NMR (119 MHz, CDCl.sub.3) -2.0.

Example 7Synthesis of Compound (7)

[0144] ##STR00057##

[0145] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (760 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.35 M] pentan-3-ylzinc bromide (740 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet Et.sub.2O (3 mL) and H.sub.2O (3 mL) via syringe and worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound 7 as a clear oil (192 mg, 93%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.53-7.49 (m, 2H), 7.36-7.32 (m, 3H), 1.57-1.47 (m, 2H), 1.36 (dp, J=14.7, 7.4 Hz, 2H), 0.87 (t, J=7.4 Hz, 6H), 0.74-0.68 (m, 1H), 0.28 (s, 6H); .sup.13C NMR (151 MHz, CDCl.sub.3) 139.7, 133.8, 128.6, 127.6, 28.9, 21.7, 13.7, 3.6; .sup.29Si NMR (119 MHz, CDCl.sub.3) 1.04; FTIR (cm.sup.1):3069, 2959, 2871, 1427, 1248, 1029, 831, 810, 700, 471. HRMS (CI) m/z, calculated for [C.sub.13H.sub.22Si].sup.+: 206.1491; found: 206.1495.

Example 8Synthesis of Compound (8)

[0146] ##STR00058##

[0147] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (500 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.00 M] 1-octylethylzinc bromide (1 mL, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with dry THF (405 L, 5 equiv, 5 mmol) via syringe and allowed to stir 15 minutes at RT then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (8) as a clear oil (261 mg, 94%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.51-7.48 (m, 2H), 7.36-7.31 (m, 3H), 1.49-1.36 (m, 2H), 1.33-1.20 (m, 9H), 1.19-1.13 (m, 2H), 1.13-1.06 (m, 1H), 0.92 (d, J=7.2 Hz, 3H), 0.88 (t, J=7.1 Hz, 3H), 0.86-0.80 (m, 1H), 0.24 (d, J=2.6 Hz, 6H); .sup.13C NMR (151 MHz, CDCl.sub.3) 139.1, 134.1, 128.8, 127.7, 32.1, 31.7, 29.8, 29.7, 29.5, 28.7, 22.8, 19.2, 14.3, 14.2, 4.7; .sup.29Si NMR (119 MHz, CDCl.sub.3) 0.17; FTIR (cm.sup.1): 3069, 2955, 2924, 2853, 1466, 1427, 1248, 1112, 832, 813, 770, 733, 700. HRMS (CI) m/z, calculated for [C.sub.18H.sub.31Si].sup.+: 275.2195; found: 275.2206.

Example 9Synthesis of Compound (9)

[0148] ##STR00059##

[0149] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (400 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [0.91 M] (4-methylpentan-2-yl)zinc bromide in dioxane (1.10 mL, 1 mmol) were combined under N.sub.2 and stirred at RT for 15 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe and worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (9) as a clear volatile oil (170.1 mg, 77%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.52-7.49 (m, 2H), 7.37-7.33 (m, 3H), 1.67 (ttd, J=13.2, 6.6, 4.4 Hz, 1H), 1.16 (ddd, 2=13.4, 9.7, 3.6 Hz, 1H), 1.09 (ddd, J=13.5, 10.8, 4.4 Hz, 1H), 1.00-0.94 (m, 1H), 0.90 (d, J=7.0 Hz, 3H), 0.86 (d, J=6.6 Hz, 3H), 0.79 (d, J=6.5 Hz, 3H), 0.25 (s, 3H), 0.24 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 138.9, 134.1, 128.8, 127.7, 40.9, 25.5, 24.1, 21.1, 16.5, 14.0, 4.8, 4.9; .sup.29Si NMR (119 MHz, CDCl.sub.3) (0.16; FTIR (cm-1): 2954, 2900, 2867, 1248, 1112, 830, 767, 733, 699. HRMS (CI) m/z, calculated for [C.sub.13H.sub.21Si].sup.+: 205.1413; found: 205.1419.

Example 10Synthesis of Compounds (10-exo) and (10-endo)

[0150] ##STR00060##

[0151] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (690 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.23 M] (1S,4R)-bicyclo[2.2.1]heptan-2ylzinc bromide (810 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet Et.sub.2O (3 mL) and H.sub.2O (3 mL) via syringe and worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compounds (10-exo) and (10-endo) as an inseparable mixture of exo:endo (80:20) diastereomers as a clear oil (230 mg, 99%). Useful diagnostic peaks for each compound are listed: (10-exo): .sup.1H NMR (600 MHz, CDCl.sub.3) 2.21 (dd, J=3.7, 2.0 Hz, 2H), 1.06-1.05 (m, 2H), 0.84-0.78 (m, 1H), 0.24 (s, 3H), 0.22 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 139.6, 134.1, 128.8, 127.8, 38.1, 37.9, 37.1, 34.5, 32.9, 29.1, 28.8, 3.9, 3.9; .sup.29Si NMR (119 MHz, CDCl.sub.3) 3.23. (10-endo): .sup.1H NMR (600 MHz, CDCl.sub.3) 2.33-2.25 (m, 2H), 1.78-1.69 (m, 1H), 1.03-0.98 (m, 1H), 0.31 (s, 3H), 0.29 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 140.4, 133.9, 128.7, 127.8, 41.9, 39.8, 37.3, 32.0, 30.0, 28.6, 27.6, 2.7, 2.9; .sup.29Si NMR (119 MHz, CDCl.sub.3) 2.81.

[0152] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 16 mg, 10 mol), Et.sub.2O (970 L), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [1.21 M] (1S,4R)-bicyclo[2.2.1]heptan-2-ylmagnesium bromide (830 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compounds (10-exo) and (10-endo) as an inseparable mixture of exo:endo (73:27) diastereomers as a clear oil (150 mg, 65%). Useful diagnostic peaks for each compound are listed:(10-exo): .sup.1H NMR (600 MHz, CDCl.sub.3) 2.22-2.20 (m, 2H), 1.06-1.05 (m, 2H), 0.83-0.79 (m, 1H), 0.24 (s, 3H), 0.22 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 139.5, 134.0, 128.8, 127.8, 38.1, 37.9, 37.1, 34.5, 32.9, 29.0, 28.7, 3.9, 3.9, .sup.29Si NMR (119 MHz, CDCl.sub.3) -3.20. (10-endo): .sup.1H NMR (600 MHz, CDCl.sub.3) 2.31 (s, 1H), 2.27 (t, J=4.3 Hz, 1H), 1.77-1.70 (m, 1H), 1.02 (tdd, J=11.0, 4.9, 2.0 Hz, 1H), 0.31 (s, 3H), 0.28 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 140.4, 133.9, 128.7, 127.8, 41.9, 39.7, 37.3, 32.0, 30.0, 28.5, 27.6, 2.7, 3.0, .sup.29Si NMR (119 MHz, CDCl.sub.3) 2.78.

Example 11Synthesis of Compound (11)

[0153] ##STR00061##

[0154] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (260 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [0.80 M] -methylbenzylzinc bromide in dioxane (1.25 mL, 1 mmol) were combined under N.sub.2 and stirred at RT for 16 h. The reaction was quenched with THF (0.4 mL), stirred for 15 min, and then wet EtOAc (0.5 mL) and brine (3 mL) were added via syringe and worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford 233 mg of mixture: compound (11), DL-2,3-diphenylbutane, meso-2,3-diphenylbutane, and (PhMe.sub.2Si).sub.2O in a relative ratio 78:8:5:9. This mixture was purified by reverse phase chromatography on Biotage instrument using SNAP Ultra C.sub.18 120 g column (50:50 MeCN:H.sub.2O to 80:20 MeCN:H.sub.2O linear gradient) to obtain compound (11) as a colorless oil (171.1 mg, 71%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.43-7.29 (m, 5H), 7.20 (t, J=7.7 Hz, 2H), 7.09 (t, J=7.3 Hz, 1H), 6.95 (d, J=7.3 Hz, 2H), 2.39 (q, J=7.5 Hz, 1H), 1.35 (d, J=7.5 Hz, 3H), 0.25 (s, 3H), 0.21 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 145.4, 137.8, 134.3, 129.1, 128.1, 127.7, 127.5, 124.6, 29.7, 15.3, 4.2, 5.3; .sup.29Si NMR (119 MHz, CDCl.sub.3) 1.06; FTIR (cm.sup.1): 3023, 2957, 2870, 1495, 1450, 1427, 1248, 1112, 833, 817, 775, 735, 699. HRMS (CI) m/z, calculated for [C.sub.16H.sub.20Si].sup.+: 240.1334; found: 240.1345.

[0155] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 16 mg, 10 mol), Et.sub.2O (100 L), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.55 M] (1-phenylethyl)magnesium bromide (1.8 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then by reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitrile:water=50:50 to acetonitrile:water=75:25) to afford compound (11) as a clear oil (129 mg, 54%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.40-7.30 (m, 5H), 7.19 (t, J=7.6 Hz, 2H), 7.08 (t, J=7.3 Hz, 1H), 6.94 (d, J=7.2 Hz, 2H), 2.38 (q, J=7.5 Hz, 1H), 1.33 (d, J=7.5 Hz, 3H), 0.24 (s, 3H), 0.19 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 145.2, 137.5, 134.1, 129.0, 127.9, 127.5, 127.3, 124.4, 29.5, 15.1, 4.4, 5.5, .sup.29Si NMR (119 MHz, CDCl.sub.3) 1.03.

Example 12Synthesis of Compound (12)

[0156] ##STR00062##

[0157] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (745 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.32 M] (4-phenylbutan-2-yl)zinc bromide (760 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with dry THF (405 L, 5 equiv, 5 mmol) via syringe and allowed to stir 15 minutes at RT then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (12) as a clear oil (267 mg, 99%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.49-7.46 (m, 2H), 7.36-7.30 (m, 3H), 7.24 (t, J=7.6 Hz, 2H), 7.14 (t, J=7.4 Hz, 1H), 7.11 (d, J=7.4 Hz, 2H), 2.76 (ddd, J=14.6, 10.4, 4.9 Hz, 1H), 2.46 (ddd, J=13.5, 10.1, 6.7 Hz, 1H), 1.79 (dddd, J=13.7, 10.3, 6.6, 3.5 Hz, 1H), 1.44-1.36 (m, 1H), 1.02 (d, J=7.3 Hz, 3H), 0.92 (ddp, J=11.2, 7.3, 3.7 Hz, 1H), 0.26 (s, 3H), 0.25 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 143.0, 138.6, 134.1, 128.9, 128.6, 128.4, 127.8, 125.7, 35.0, 33.9, 19.0, 14.1, 4.6, 4.8; .sup.29Si NMR (119 MHz, CDCl.sub.3) 0.08; FTIR (cm.sup.1): 3067, 3025, 2953, 2864, 1454, 1427, 1248, 1112, 833, 812, 772, 699. HRMS (CI) m/z, calculated for [C.sub.13H.sub.22Si].sup.+: 253.1413; found: 253.1403.

[0158] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), diethyl ether (1.1 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes gradient to hexanes:dichloromethane=95:5) to afford compound (12) as a clear oil (264 mg, 98%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.50-7.47 (m, 2H), 7.37-7.31 (m, 3H), 7.24 (t, J=7.5 Hz, 2H), 7.17-7.13 (m, 1H), 7.11 (d, J=7.5 Hz, 2H), 2.76 (ddd, J=14.0, 10.4, 4.9 Hz, 1H), 2.46 (ddd, J=13.6, 10.1, 6.7 Hz, 1H), 1.79 (dddd, J=13.7, 10.3, 6.7, 3.6 Hz, 1H), 1.41 (dtd, J=13.6, 10.3, 4.9 Hz, 1H), 1.02 (d, J=7.2 Hz, 3H), 0.96-0.89 (m, 1H), 0.26 (s, 3H), 0.25 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.0, 138.7, 134.1, 128.9, 128.6, 128.4, 127.8, 125.7, 35.0, 33.9, 19.0, 14.1, 4.6, 4.8, .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.05.

Example 13Synthesis of Compound (13)

[0159] ##STR00063##

[0160] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (580 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.09 M] 4-(4-(ethoxycarbonyl)phenyl)butan-2yl)zinc bromide (920 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe and worked up according to general procedure B and purified via silica gel flash chromatography (hexanes:dichloromethane=90:10 gradient to hexanes:dichloromethane=80:20) and product dried (50 C./0.1 mmHg) for 43 h to afford compound (13) as a clear oil (276.1 mg, 81%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.94 (d, J=8.2 Hz, 2H), 7.49-7.43 (m, 2H), 7.39-7.30 (m, 3H), 7.16 (d, J=8.2 Hz, 2H), 4.37 (q, J=7.1 Hz, 2H), 2.80 (ddd, J=14.3, 9.9, 4.9 Hz, 1H), 2.52 (ddd, J=13.6, 9.7, 7.0 Hz, 1H), 1.80 (dddd, J=13.5, 10.2, 7.0, 3.5 Hz, 1H), 1.48-1.39 (m, 1H), 1.39 (t, J=7.1 Hz, 3H), 1.02 (d, J=7.2 Hz, 3H), 0.89 (dtq, J=14.9, 7.6, 3.4 Hz, 1H), 0.26 (s, 3H), 0.25 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 166.8, 148.4, 138.4, 134.0, 129.7, 129.0, 128.5, 128.0, 127.8, 60.9, 34.9, 33.5, 18.8, 14.5, 14.0, 4.6, 5.0; .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.04; FTIR (cm.sup.1): 2954, 2864, 2361, 2340, 1427, 1718, 1610, 1275, 1248, 1107, 1021, 833, 701. HRMS (CI) m/z, calculated for [C.sub.21H.sub.29O.sub.2Si]: 341.1937; found: 341.1926.

Example 14Synthesis of Compound (14)

[0161] ##STR00064##

[0162] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (710 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.26 M] (4-(4-methoxyphenyl)butan-2yl)zinc bromide (795 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet Et.sub.2O (3 mL) and H.sub.2O (3 mL) via syringe and worked up according to general procedure B and purified via silica gel flash chromatography (hexanes:DCM=85:15) to afford compound (14) as a clear oil (257 mg, 86%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.50-7.44 (m, 2H), 7.38-7.30 (m, 3H), 7.03 (d, J=8.5 Hz, 2H), 6.81 (d, J=8.6 Hz, 2H), 3.79 (s, 3H), 2.71 (ddd, J=14.4, 10.2, 4.8 Hz, 1H), 2.41 (ddd, J=13.7, 9.9, 6.9 Hz, 1H), 1.82-1.73 (m, 1H), 1.42-1.34 (m, 1H), 1.01 (d, J=7.3 Hz, 3H), 0.94-0.85 (m, 1H), 0.25 (s, 3H), 0.24 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 157.8, 138.7, 135.1, 134.1, 129.4, 128.9, 127.8, 113.9, 55.4, 34.08, 34.07, 18.9, 14.1, 4.6, 4.8; .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.08; FTIR (cm.sup.1): 3068, 2998, 2952, 2864, 1612, 1512, 1246, 1177, 1113, 1038, 816, 771, 735, 702. HRMS (CI) m/z, calculated for [C.sub.19H.sub.26OSi].sup.+: 298.1753; found: 298.1741.

[0163] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), diethyl ether (620 L), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.85 M] (4-(4-methoxyphenyl)butan-2-yl)magnesium bromide (1.18 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes gradient to hexanes:dichloromethane=90:10) to afford compound (14) as a clear oil (283 mg, 95%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.50-7.46 (m, 2H), 7.36-7.31 (m, 3H), 7.02 (d, J=8.6 Hz, 2H), 6.78 (d, 3=8.6 Hz, 2H), 3.75 (s, 3H), 2.70 (ddd, J=14.5, 10.2, 4.9 Hz, 1H), 2.40 (ddd, J=13.6, 10.0, 6.8 Hz, 1H), 1.74 (dddd, J=13.6, 10.2, 6.8, 3.5 Hz, 1H), 1.40-1.33 (m, 1H), 1.00 (d, J=7.3 Hz, 3H), 0.90 (dqd, J=11.0, 7.6, 7.2, 3.5 Hz, 1H), 0.25 (s, 3H), 0.24 (s, 3H), .sup.13C NMR (151 MHz, CD.sub.2Cl.sub.2) 158.3, 139.2, 135.5, 134.5, 129.8, 129.3, 128.1, 114.1, 55.7, 34.6, 34.4, 19.3, 14.3, 4.5, 4.7, .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.17.

Example 15Synthesis of Compound (15)

[0164] ##STR00065##

[0165] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (700 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.25 M] (4-(4-chlorophenyl)butan-2-yl)zinc bromide (800 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with dry THF (405 L, 5 equiv, 5 mmol) via syringe and allowed to stir 15 minutes at RT then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (15) as a clear oil (285 mg, 94%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.46 (dd, J=7.3, 1.9 Hz, 2H), 7.34 (q, J=5.6 Hz, 3H), 7.21 (d, J=8.3 Hz, 2H), 7.02 (d, J=8.3 Hz, 2H), 2.71 (ddd, J=14.3, 10.0, 4.9 Hz, 1H), 2.43 (ddd, J=13.7, 9.7, 7.0 Hz, 1H), 1.76 (dddd, J=13.5, 10.2, 7.0, 3.5 Hz, 1H), 1.42-1.34 (m, 1H), 1.01 (d, J=7.3 Hz, 3H), 0.87 (dqd, J=10.9, 7.3, 3.5 Hz, 1H), 0.25 (s, 3H), 0.24 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 141.4, 138.5, 134.1, 131.4, 129.9, 129.0, 128.5, 127.8, 34.3, 33.8, 18.9, 14.1, 4.6, 4.9; .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.05; FTIR (cm.sup.1):3068, 2953, 2864, 1492, 1427, 1248, 1111, 1092, 1015, 831, 812, 701, 522, 472. HRMS (CI) m/z, calculated for [C.sub.18H.sub.22SiCl].sup.+: 301.1179; found: 301.1166.

[0166] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), diethyl ether (0.52 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.79 M] 4-(4-(chloro)phenyl)butan-2-yl)magnesium bromide (1.28 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then by reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitrile:water=50:50 to acetonitrile:water 100:0) to afford compound (15) as a clear oil (272 mg, 89%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.52-7.43 (m, 2H), 7.40-7.32 (m, 3H), 7.22 (d, J=8.4 Hz, 2H), 7.03 (d, J=8.3 Hz, 2H), 2.76-2.69 (m, 1H), 2.44 (ddd, J=13.7, 9.7, 7.0 Hz, 1H), 1.77 (dddd, J=13.5, 10.2, 7.0, 3.5 Hz, 1H), 1.40 (dtd, J=13.9, 10.1, 4.9 Hz, 1H), 1.02 (d, J=7.3 Hz, 3H), 0.94-0.83 (m, 1H), 0.27 (s, 3H), 0.26 (s, 3H). .sup.13C NMR (151 MHz, CDCl.sub.3) 141.4, 138.6, 134.1, 131.5, 129.9, 129.0, 128.5, 127.8, 34.3, 33.8, 18.9, 14.1, 4.6, 4.9. .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.05.

Example 16Synthesis of Compound (16)

[0167] ##STR00066##

[0168] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (640 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.14 M] (4-(4-(trifluoromethyl)phenyl)butan-2yl)zinc bromide (880 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 8 h. The reaction was quenched with THF (405 L, 5 equiv, 5 mmol) via syringe and allowed to stir 15 minutes at RT then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes:ethyl acetate=99:1) and product dried (45 C./0.1 mmHg) for 7 h to afford compound (16) as a clear oil (276.1 mg, 81%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.50 (d, J=8.0 Hz, 2H), 7.48-7.44 (m, 2H), 7.39-7.31 (m, 3H), 7.19 (d, J=8.0 Hz, 2H), 2.80 (ddd, J=14.4, 10.1, 5.0 Hz, 1H), 2.51 (ddd, J=13.6, 9.8, 6.9 Hz, 1H), 1.79 (dddd, J=13.6, 10.2, 6.9, 3.5 Hz, 1H), 1.47-1.36 (m, 1H), 1.02 (d, J=7.2 Hz, 3H), 0.89 (ddp, J=11.4, 7.6, 3.8 Hz, 1H), 0.26 (s, 3H), 0.25 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 147.0, 138.4, 134.0, 129.0, 128.8, 128.0 (q, J=32.2 Hz), 127.8, 125.3 (q, J=3.8 Hz), 124.5 (q, J=271.9 Hz), 34f.8, 33.6, 18.9, 14.1, 4.6, 5.0; .sup.19F NMR (376 MHz, CDCl.sub.3) 5-62.22; .sup.29Si NMR (119 MHz, CDCl.sub.3) 5-0.03; FTIR (cm.sup.1): 2954, 2866, 2361, 1618, 1427, 1326, 1249, 1163, 1124, 1068, 1018, 814, 701. HRMS (CI) m/z, calculated for [C.sub.15H.sub.20F.sub.3Si].sup.+: 321.1286; found: 321.1271.

Example 17Synthesis of Compound (17)

[0169] ##STR00067##

[0170] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (780 L), triethylamine (140 L, 1 mmol), trimethylsilyl iodide (290 L, 2 mmol), and [1.25 M] (4-(4-chlorophenyl)butan-2-yl)zinc bromide (800 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet Et.sub.2O (3 mL) and H.sub.2O (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (17) as a clear oil (232 mg, 96%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.25-7.22 (m, 2H), 7.13-7.08 (m, 2H), 2.76 (ddd, J=14.4, 10.1, 4.8 Hz, 1H), 2.47 (ddd, J=13.8, 10.1, 6.7 Hz, 1H), 1.74 (dddd, J=13.8, 10.4, 6.7, 3.6 Hz, 1H), 1.38 (dtd, J=13.5, 10.2, 4.8 Hz, 1H), 0.99 (d, J=7.3 Hz, 3H), 0.65-0.56 (m, 1H), 0.04 (d, J=1.7 Hz, 9H); .sup.13C NMR (151 MHz, CDCl.sub.3) 141.6, 131.4, 129.9, 128.5, 34.5, 34.0, 19.4, 14.0, 3.1; .sup.29Si NMR (119 MHz, CDCl.sub.3) 4.55; FTIR (cm.sup.+1): 2953, 2865, 1492, 1248, 1093, 1016, 856, 834, 747, 521. HRMS (CI) m/z, calculated for [C.sub.13H.sub.20SiCl].sup.+: 239.1023; found: 239.1026.

Example 18Synthesis of Compound (18)

[0171] ##STR00068##

[0172] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 16 mg, 10 mol), dioxane (650 L), triethylamine (140 L, 1 mmol), benzyldimethylsilyl iodide (410 L, 2 mmol), and [1.25 M] (4-(4-chlorophenyl)butan-2-yl)zinc bromide (800 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was diluted with dry THF (405 L, 5 equiv, 5 mmol) via syringe and allowed to stir 15 minutes at RT then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (18) as a clear oil (313 mg, 99%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.24 (d, J=8.3 Hz, 2H), 7.19 (t, J=7.6 Hz, 2H), 7.09 (d, J=8.3 Hz, 2H), 7.06 (t, J=7.6 Hz, 1H), 6.95 (d, J=7.5 Hz, 2H), 2.77 (ddd, J=14.3, 10.1, 4.8 Hz, 1H), 2.45 (ddd, J=13.6, 9.8, 7.0 Hz, 1H), 2.08 (s, 2H), 1.74 (dddd, J=13.4, 10.0, 6.9, 3.2 Hz, 1H), 1.43-1.35 (m, 1H), 1.01 (d, J=7.4 Hz, 3H), 0.69 (dqd, J=10.7, 7.3, 3.2 Hz, 1H), 0.08 (s, 6H); .sup.13C NMR (151 MHz, CDCl.sub.3) 141.2, 140.2, 131.3, 129.7, 128.4, 128.1, 123.9, 34.1, 33.7, 23.9, 17.8, 13.7, 5.2, 5.3; .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.24; FTIR (cm.sup.1): 3081, 3024, 2952, 2864, 1600, 1492, 1452, 1248, 1093, 1015, 830, 699. HRMS (CI) m/z, calculated for [C.sub.19H.sub.26SiCl].sup.+: 317.1492; found: 317.1490.

Example 19Synthesis of Compound (19)

[0173] ##STR00069##

[0174] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 16 mg, 10 mol), dioxane (610 L), triethylamine (140 L, 1 mmol), methyldiphenylsilyl iodide (450 L, 2 mmol), and [1.25 M] (4-(4-chlorophenyl)butan-2-yl)zinc bromide (800 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with dry THF (405 L, 5 equiv, 5 mmol) via syringe and allowed to stir 15 minutes at RT then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (19) as a clear oil (291 mg, 80%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.49-7.45 (m, 4H), 7.41-7.30 (m, 6H), 7.22 (d, J=8.3 Hz, 2H), 7.01 (d, J=8.2 Hz, 2H), 2.75 (ddd, J=13.9, 9.4, 4.8 Hz, 1H), 2.47 (dt, J=13.7, 8.4 Hz, 1H), 1.91-1.79 (m, 1H), 1.49-1.40 (m, 1H), 1.35-1.23 (m, 1H), 1.08 (d, J=7.3 Hz, 3H), 0.52 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 141.0, 136.4, 136.2, 134.8, 134.8, 131.3, 129.8, 129.1, 129.1, 128.3, 127.8, 127.8, 34.0, 33.6, 17.0, 14.1, 6.4; .sup.29Si NMR (119 MHz, CDCl.sub.3) 4.70; FTIR (cm.sup.1): 3068, 2952, 2864, 1491, 1427, 1252, 1111, 1015, 788, 737, 700, 490, 477. HRMS (CI) m/z, calculated for [C.sub.23H.sub.24SiCl].sup.+: 363.1336; found: 363.1320.

Example 20Synthesis of Compound (20)

[0175] ##STR00070##

[0176] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (700 L), triethylamine (140 L, 1 mmol), triethylsilyl iodide (360 L, 2 mmol), and [1.25 M] (4-(4-chlorophenyl)butan-2-yl)zinc bromide (800 L, 1 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet Et.sub.2O (3 mL) and H.sub.2O (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (20) as a clear oil (85 mg, 30%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.24 (d, J=8.3 Hz, 2H), 7.10 (d, J=8.3 Hz, 2H), 2.79 (ddd, J=14.3, 10.2, 4.8 Hz, 1H), 2.45 (ddd, J=13.6, 9.9, 6.9 Hz, 1H), 1.75 (dddd, J=13.4, 10.0, 6.9, 3.1 Hz, 1H), 1.46-1.38 (m, 1H), 1.02 (d, J=7.4 Hz, 3H), 0.92 (t, J=7.9 Hz, 9H), 0.82-0.74 (m, 1H), 0.53 (q, J=7.9 Hz, 6H); .sup.13C NMR (151 MHz, CDCl.sub.3) 141.6, 131.4, 129.9, 128.5, 34.6, 34.2, 16.5, 14.2, 7.8, 2.3; .sup.29Si NMR (119 MHz, CDCl.sub.3) 8.20; FTIR (cm.sup.1): 2952, 2909, 874, 1492, 1456, 1239, 1093, 1016, 834, 806, 732, 521. HRMS (CI) m/z, calculated for [C.sub.14H.sub.22SiCl].sup.+: 253.1179; found: 253.1177.

Example 21Synthesis of Compound (21)

[0177] ##STR00071##

[0178] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (500 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [1.05 M] (3-methylbutan-2-yl)zinc iodide in dioxane (1.00 mL, 1.05 mmol) were combined under N.sub.2 and stirred at RT for 4 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford compound (21) as a clear volatile oil (175.1 mg, 81%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.54-7.51 (m, 2H), 7.37-7.33 (m, 3H), 1.87 (heptd, J=6.8, 3.4 Hz, 1H), 0.94-0.89 (m, 7H), 0.81 (d, J=6.9 Hz, 3H), 0.30 (s, 3H), 0.29 (s, 3H); .sup.13C NMR (151 MHz, CDCl.sub.3) 139.9, 134.0, 128.7, 127.8, 29.0, 26.8, 23.2, 19.9, 9.7, 3.2, 3.3; .sup.29Si NMR (119 MHz, CDCl.sub.3) -0.85; FTIR (cm.sup.1): 2955, 2871, 1465, 1427, 1248, 1111, 834, 817, 768, 733, 700. HRMS (CI) m/z, calculated for [C.sub.13H.sub.22Si].sup.+: 206.1491; found: 206.1482.

Example 22Synthesis of Compounds (22) and (23)

[0179] ##STR00072##

[0180] According to general procedure A, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), dioxane (60 L), triethylamine (140 L, 1 mmol), dimethylphenylsilyl iodide (360 L, 2 mmol), and [0.54 M] (3,3-dimethylbutan-2-yl)zinc iodide (1.85 mL, 1 mmol) were combined under N.sub.2 and stirred at RT for 8 h. The reaction was quenched with wet EtOAc (0.5 mL) and brine (3 mL) via syringe then worked up according to general procedure B and purified via silica gel flash chromatography (hexanes) to afford an inseparable mixture of isomers (22):(23) (62:38) as a clear oil (123.0 mg, 56%): Useful diagnostic peaks for each compound are listed. (22): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.56-7.50 (m, 2H), 7.38-7.31 (m, 3H), 0.98-0.92 (m, 4H), 0.89 (s, 9H), 0.36 (s, 3H), 0.32 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) 141.2, 134.0, 128.6, 127.7, 33.7, 32.3, 30.3, 11.9, 0.5, 2.0; .sup.29Si NMR (119 MHz, CDCl.sub.3) -2.06. HRMS (CI) m/z, calculated for [C.sub.13H.sub.21Si].sup.+: 205.1413; found: 205.1407. (23): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.55-7.50 (m, 2H), 7.38-7.31 (m, 3H), 1.22-1.15 (m, 2H), 0.85 (s, 9H), 0.72-0.65 (m, 2H), 0.25 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 139.8, 133.7, 128.9, 127.8, 37.9, 31.2, 28.9, 9.8, 3.0; .sup.29Si NMR (119 MHz, CDCl.sub.3) 2.21. HRMS (CI) m/z, calculated for [C.sub.13H.sub.21Si].sup.+: 205.1413; found: 205.1406. (22)+(23): FTIR (cm.sup.1): 2955, 2911, 1466, 1427, 1363, 1249, 1112, 834, 815, 700.

Example 23Synthesis of Compound (24)

[0181] ##STR00073##

[0182] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (0.3 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.67 M] 3-pentylmagnesium bromide (1.50 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, the crude product was purified via silica gel flash chromatography (hexanes) to afford compound (24) as a clear oil (203 mg, 99%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.55-7.50 (m, 2H), 7.38-7.34 (m, 3H), 1.54 (dqd, J=14.7, 7.5, 5.3 Hz, 2H), 1.38 (dp, J=14.7, 7.4 Hz, 2H), 0.88 (t, J=7.4 Hz, 6H), 0.72 (tt, J=7.5, 5.1 Hz, 1H), 0.29 (s, 6H). .sup.13C NMR (151 MHz, CDCl.sub.3) 139.8, 134.0, 128.8, 127.8, 29.04, 21.9, 13.8, 3.4. .sup.29Si NMR (119 MHz, CDCl.sub.3) 1.0.

Example 24Synthesis of Compound (25)

[0183] ##STR00074##

[0184] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), diethyl ether (0.76 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.96 M](trimethylsilyl)methylmagnesium chloride (1.04 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (25) as a clear oil (122 mg, 55%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.59-7.48 (m, 2H), 7.38-7.33 (m, 3H), 0.31 (s, 6H), 0.02 (s, 2H), 0.01 (s, 9H). .sup.13C NMR (151 MHz CDCl.sub.3) 141.5, 133.4, 128.86, 127.8, 3.4, 1.4, 0.0. .sup.29Si NMR (119 MHz, CDCl.sub.3) 0.5, 4.2. FTIR (cm.sup.1): 2953, 2897, 1426, 1250, 1113, 1051, 836, 698. HRMS (CI) m/z, calculated for [C.sub.1NH.sub.19Si.sub.2].sup.+[MCH.sub.3].sup.+: 207.1025; found: 207.1027.

Example 25Synthesis of Compound (26)

[0185] ##STR00075##

[0186] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (750 L), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.95 M] neopentylmagnesium bromide (1.05 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (26) as a clear oil (205 mg, 99%): 1H NMR (400 MHz, CDCl.sub.3) 7.55-7.52 (m, 2H), 7.42-7.29 (m, 3H), 0.95 (s, 11H), 0.35 (s, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) 141.0, 133.6, 128.7, 127.8, 33.2, 33.2, 31.3, 0.4. .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.7. FTIR (cm.sup.1): 2954, 2893, 2869, 1465, 1427, 1363, 1249, 1113, 832, 707. HRMS (CI) m/z, calculated for [C.sub.13H.sub.22Si].sup.+[M].sup.+: 206.1491; found: 206.1501.

Example 26Synthesis of Compound (27)

[0187] ##STR00076##

[0188] According to general procedure B, (DrewPhos).sub.2PdI.sub.2(16 mg, 10 mol), Et.sub.2O (50 L), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.40 M] 2-methyl-2-phenylpropylmagnesium chloride (2.50 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (27) as a clear oil (136.2 mg, 51%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.42-7.37 (m, 2H), 7.33-7.32 (m, 2H), 7.30-7.27 (m, 3H), 7.27-7.22 (m, 2H), 7.15-7.13 (m, 1H), 1.37 (s, 2H), 1.32 (s, 6H), 0.01 (s, 6H). .sup.13C NMR (151 MHz, CDCl.sub.3) 151.1, 140.8, 133.6, 128.7, 128.1, 127.8, 125.7, 125.6, 37.5, 34.2, 32.6, 1.2. .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.7. FTIR (cm.sup.1): 2959, 2360, 2339, 1652, 1558, 1456, 1110, 826. 668. HRMS (CI) m/z, calculated for C.sub.17H.sub.21Si.sup.+[MCH.sub.3].sup.+: 253.1413; found: 253.1417.

Example 27Synthesis of Compound (28)

[0189] ##STR00077##

[0190] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.40 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [2.62 M]phenylmagnesium bromide (400 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then by reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitrile:water=50:50 to acetonitrile:water=100:0) to afford compound (28) as a clear oil (215 mg, 97%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.61-7.50 (m, 4H), 7.40-7.35 (m, 6H), 0.59 (s, 6H). .sup.13C NMR (151 MHz, CDCl.sub.3) 138.4, 134.4, 129.2, 128.0, 2.2. .sup.29Si NMR (119 MHz, CDCl.sub.3) 8.1.

Example 28Synthesis of Compound (29)

[0191] ##STR00078##

[0192] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.3 mL), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [2.0 M] ortho-tolylmagnesium bromide (0.500 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (29) as a clear oil (210 mg, 93%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.51-7.47 (m, 3H), 7.38-7.31 (m, 3H), 7.29 (td, J=7.5, 1.3 Hz, 1H), 7.18 (t, J=7.4 Hz, 1H), 7.14 (d, J=7.6 Hz, 1H), 2.25 (s, 3H), 0.58 (s, 6H), .sup.13C NMR (151 MHz, CD.sub.2Cl.sub.2) 144.7, 139.7, 136.8, 135.9, 134.6, 130.4, 130.1, 129.5, 128.4, 125.5, 23.5, 1.0, .sup.29Si NMR (119 MHz, CDCl.sub.3) -8.1, FTIR (cm.sup.1): 3067, 3050, 3003, 2956, 1589, 1428, 1250, 1130, 1112, 817, 775, 701, 642, 474. HRMS (CI) m/z, calculated for C.sub.14H.sub.15Si.sup.+[M].sup.+: 211.0943; found: 211.0952.

Example 29Synthesis of Compound (30)

[0193] ##STR00079##

[0194] According to general procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (720 L), dimethylphenylsilyl chloride (200 L, 1.2 mmol), and [0.93 M] 2-mesitylmagnesium bromide (1.08 mL, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (30) as a clear oil (250 mg, 98%): 1H NMR (400 MHz, CDCl.sub.3) 7.52-7.44 (m, 2H), 7.35-7.29 (m, 3H), 6.84 (s, 2H), 2.30 (s, 6H), 2.29 (s, 3H), 0.63 (s, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) 145.2, 141.7, 139.2, 133.5, 130.8, 129.3, 128.7, 128.0, 25.1, 21.1, 3.2. .sup.29Si NMR (119 MHz, CDCl.sub.3) 9.0. FTIR (cm.sup.1): 2954, 1605, 1450, 1427, 1250, 1105, 816, 701, 667. HRMS (CI) m/z, calculated for C.sub.17H.sub.22Si [M].sup.+: 254.1491; found: 254.1495.

Example 30Synthesis of Compound (31)

[0195] ##STR00080##

[0196] According to procedure B, (DrewPhos).sub.2PdI.sub.2(16 mg, 10 mol), Et.sub.2O (1.04 mL), trimethylsilyl chloride (150 L, 1.2 mmol), and [1.43 M] (4-phenylbutan-2-yl)magnesium bromide (700 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (31) as a clear oil (154 mg, 75%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.29 (t, J=7.6 Hz, 2H), 7.21-7.16 (m, 3H), 2.81 (ddd, J=14.8, 10.6, 4.9 Hz, 1H), 2.51 (ddd, J=13.5, 10.3, 6.6 Hz, 1H), 1.79 (dddd, J=13.9, 10.3, 6.5, 3.7 Hz, 1H), 1.49-1.33 (m, 1H), 1.01 (d, J=7.4 Hz, 3H), 0.65 (dqd, J=10.9, 7.4, 3.7 Hz, 1H), 0.03 (s, 9H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.3, 128.6, 128.4, 125.7, 35.2, 34.1, 19.6, 14.0, 3.1, .sup.29Si NMR (119 MHz, CDCl.sub.3) 4.53, FTIR (cm.sup.1): 3027, 2953, 2865, 1604, 1496, 1454, 1248, 856, 834, 745, 698. HRMS (CI) m/z, calculated for [C.sub.13H.sub.21Si].sup.+: 205.1413; found: 205.1418.

Example 31Synthesis of Compound (32)

[0197] ##STR00081##

[0198] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (950 L), phenethyldimethylsilyl chloride (240 L, 1.2 mmol), and [1.23 M] (4-phenylbutan-2-yl)magnesium bromide (810 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then by reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitrile:water=75:25 to acetonitrile:water=95:0) to afford compound (32) as a clear oil (280 mg, 94%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.29-7.23 (m, 4H), 7.22-7.12 (m, 6H), 2.82 (ddd, J=14.3, 10.5, 4.8 Hz, 1H), 2.59 (dd, J=11.4, 6.1 Hz, 2H), 2.50 (ddd, J=13.6, 10.1, 6.7 Hz, 1H), 1.84-1.76 (m, 1H), 1.47-1.39 (m, 1H), 1.04 (d, J=7.4 Hz, 3H), 0.90-0.85 (m, 2H), 0.78-0.70 (m, 1H), 0.01 (s, 6H), .sup.13C NMR (151 MHz, CDCl.sub.3) 145.5, 143.1, 128.6, 128.4, 127.9, 125.8, 125.7, 35.2, 34.1, 30.2, 18.5, 16.1, 14.0, 4.98, 5.00, .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.5. HRMS (CI) m/z, calculated for [C.sub.19H.sub.25Si].sup.+: 281.1726; found: 281.1716.

Example 32Synthesis of Compound (33)

[0199] ##STR00082##

[0200] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (930 L), (3,3-dimethylbutyl)dimethylsilyl chloride (250 L, 1.2 mmol), and [1.23 M] (4-phenylbutan-2-yl)magnesium bromide (810 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then by reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitrile:water=75:25 to acetonitrile:water=100:0) to afford compound (33) as a clear oil (255 mg, 92%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.28 (t, J=7.6 Hz, 2H), 7.21-7.16 (m, 3H), 2.82 (ddd, J=14.1, 10.4, 4.8 Hz, 1H), 2.50 (ddd, J=13.5, 10.1, 6.7 Hz, 1H), 1.78 (dddd, J=13.7, 10.3, 6.7, 3.5 Hz, 1H), 1.46-1.37 (m, 1H), 1.11 (ddd, J=12.7, 5.8, 2.1 Hz, 2H), 1.01 (d, J=7.4 Hz, 3H), 0.84 (s, 9H), 0.74-0.66 (m, 1H), 0.45-0.40 (m, 2H), 0.07 (s, 3H), 0.07 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.2, 128.6, 128.4, 125.7, 38.0, 35.2, 34.1, 31.2, 29.0, 18.4, 14.1, 7.8, 5.1, .sup.29Si NMR (119 MHz, CDCl.sub.3) 6.14, FTIR (cm.sup.1): 3027, 2952, 2913, 2865, 1604, 1466, 1454, 1363, 1248, 1159, 886, 835, 745, 698. HRMS (CI) m/z, calculated for [C.sub.17H.sub.29Si].sup.+: 261.2039; found: 261.2038.

Example 33Synthesis of Compound (34)

[0201] ##STR00083##

[0202] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.23 mL), (3,3,3-trifluoropropyl)dimethylsilyl chloride (210 L, 1.2 mmol), and [1.78 M] (4-phenylbutan-2-yl)magnesium bromide (560 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (34) as a clear oil (234 mg, 81%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.29 (t, J=7.6 Hz, 2H), 7.21-7.15 (m, 3H), 2.83 (ddd, J=14.2, 10.1, 4.8 Hz, 1H), 2.51 (ddd, J=13.6, 9.8, 6.9 Hz, 1H), 2.03-1.89 (m, 2H), 1.77 (dddd, J=13.6, 10.2, 6.9, 3.3 Hz, 1H), 1.49-1.39 (m, 1H), 1.03 (d, J=7.4 Hz, 3H), 0.78-0.66 (m, 3H), 0.01 (s, 3H), 0.01 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 142.7, 128.5, 128.5, 127.80 (q, J=276.7 Hz) 125.9, 34.9, 33.8, 28.95 (q, J=29.8 Hz), 18.0, 13.8, 5.5, 5.3, 5.4, .sup.19F NMR (565 MHz, C CDCl.sub.3) 68.78, .sup.29Si NMR (119 MHz, CDCl.sub.3) 6.11, FTIR (cm.sup.1): 3028, 2953, 2867, 1604, 1497, 1364, 1264, 1212, 1125, 1067, 900, 844, 699. HRMS (CI) m/z, calculated for [C.sub.15H.sub.24F.sub.3Si].sup.+: 289.1599; found: 289.1587.

Example 34Synthesis of Compound (35)

[0203] ##STR00084##

[0204] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.1 mL), chloromethyldimethylsilyl chloride (160 L, 1.2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (35) as a clear oil (154 mg, 64%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.29 (t, J=7.7 Hz, 2H), 7.21-7.16 (m, 3H), 2.81 (s, 3H), 2.52 (ddd, J=13.5, 10.3, 6.5 Hz, 1H), 1.80 (dddd, J=13.9, 10.3, 6.5, 3.6 Hz, 1H), 1.51-1.42 (m, 1H), 1.05 (d, J=7.4 Hz, 3H), 0.90 (dqd, J=11.1, 7.3, 3.6 Hz, 1H), 0.10 (s, 3H), 0.09 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 142.7, 128.5, 128.5, 125.9, 35.0, 33.8, 29.5, 17.6, 13.9, 6.0, 6.1, .sup.29Si NMR (119 MHz, CDCl.sub.3) 6.21, FTIR (cm.sup.1): 3027, 2954, 2927, 2865, 1604, 1496, 1454, 1251, 842, 746, 699. HRMS (CI) m/z, calculated for [C.sub.13H.sub.22ClSi].sup.+: 241.1179; found: 241.1182.

Example 35Synthesis of Compound (36)

[0205] ##STR00085##

[0206] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (970 L), 4-chlorobutyldimethylsilyl chloride (220 L, 1.2 mmol), and [1.23 M] (4-phenylbutan-2-yl)magnesium bromide (810 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (36) as a clear oil (247 mg, 87%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.28 (dd, J=8.3, 6.9 Hz, 2H), 7.21-7.14 (m, 3H), 3.53 (t, J=6.6 Hz, 2H), 2.81 (ddd, J=13.6, 10.3, 4.8 Hz, 1H), 2.50 (ddd, J=13.5, 10.1, 6.7 Hz, 1H), 1.82-1.73 (m, 3H), 1.46-1.36 (m, 3H), 1.01 (d, J=7.4 Hz, 3H), 0.69 (dqd, J=10.8, 7.3, 3.5 Hz, 1H), 0.55-0.48 (m, 2H), 0.05 (s, 3H), 0.05 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.1, 128.6, 128.4, 125.7, 44.9, 36.4, 35.1, 34.1, 21.4, 18.5, 14.0, 13.1, 4.98, 5.01, .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.45, FTIR (cm.sup.1): 3026, 2952, 2931, 2864, 1603, 1496, 1454, 1248, 834, 747, 699. HRMS (CI) m/z, calculated for [C.sub.16H.sub.28ClSi].sup.+: 283.1649; found: 283.1658.

Example 36Synthesis of Compound (37)

[0207] ##STR00086##

[0208] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (810 L), 4-bromobutyldimethylsilyl chloride (220 L, 1.2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitle:water=70:30 to acetonitrile:water=100:0) to afford compound (37) as a clear oil (302 mg, 92%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.28 (t, J=7.6 Hz, 2H), 7.18 (d, J=6.4 Hz, 3H), 3.41 (t, J=6.8 Hz, 2H), 2.82 (ddd, J=14.7, 10.4, 4.8 Hz, 1H), 2.49 (ddd, J=13.5, 10.1, 6.7 Hz, 1H), 1.85 (p, J=6.9 Hz, 2H), 1.77 (dddd, J=13.7, 10.2, 6.7, 3.4 Hz, 1H), 1.41 (dddd, J=14.7, 10.3, 6.8, 3.5 Hz, 3H), 1.01 (d, J=7.3 Hz, 3H), 0.69 (dqd, J=10.8, 7.4, 3.4 Hz, 1H), 0.53-0.47 (m, 2H), 0.05 (s, 6H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.1, 128.6, 128.4, 125.7, 36.6, 35.1, 34.1, 33.8, 22.6, 18.4, 14.0, 12.9, 4.98, 5.01, .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.42, FTIR (cm.sup.1): 3026, 2951, 2930, 2864, 1603, 1496, 1454, 1248, 835, 748, 699. HRMS (CI) m/z, calculated for [C.sub.15H.sub.24BrSi].sup.+: 311.0831; found: 311.0842.

Example 37Synthesis of Compound (38)

[0209] ##STR00087##

[0210] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (950 L), 5-hexenyldimethylsilyl chloride (240 L, 1.2 mmol), and [1.23 M] (4-phenylbutan-2-yl)magnesium bromide (810 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitle:water=70:30 to acetonitrile:water=100:0) to afford compound (38) as a clear oil (251 mg, 91%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.31-7.26 (m, 2H), 7.20-7.15 (m, 3H), 5.80 (ddt, J=16.9, 10.2, 6.7 Hz, 1H), 4.99 (dq, J=17.1, 1.5 Hz, 1H), 4.95-4.91 (m, 1H), 2.84-2.77 (m, 1H), 2.49 (ddd, J=13.5, 10.2, 6.6 Hz, 1H), 2.04 (q, J=7.0 Hz, 2H), 1.77 (dddd, J=13.7, 10.2, 6.6, 3.5 Hz, 1H), 1.45-1.35 (m, 3H), 1.31-1.24 (m, 2H), 1.00 (d, J=7.4 Hz, 3H), 0.68 (dqd, J=10.8, 7.4, 3.5 Hz, 1H), 0.53-0.47 (m, 2H), 0.07 (s, 3H), 0.07 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.2, 139.3, 128.6, 128.4, 125.7, 114.3, 35.2, 34.1, 33.6, 33.1, 23.6, 18.6, 14.1, 13.7, 4.9, .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.31. FTIR (cm.sup.1): 3063, 3027, 2923, 2854, 1641, 1604, 1496, 1454, 1248, 909, 834, 746, 698. HRMS (CI) m/z, calculated for [C.sub.17H.sub.27Si].sup.+: 259.1882; found: 259.1882.

Example 38Synthesis of Compound (39)

[0211] ##STR00088##

[0212] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.0 mL), pentafluorophenyldimethylsilyl chloride (230 L, 1.2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (39) as a clear oil (227 mg, 63%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.25 (t, J=7.6 Hz, 2H), 7.15 (t, J=7.4 Hz, 1H), 7.12 (d, J=7.2 Hz, 2H), 2.80 (ddd, J=14.6, 10.3, 4.9 Hz, 1H), 2.49 (ddd, J=13.5, 10.0, 6.7 Hz, 1H), 1.76 (dddd, J=13.7, 10.2, 6.7, 3.4 Hz, 1H), 1.45 (dddd, J=16.9, 12.2, 8.5, 3.5 Hz, 1H), 1.09 (dp, J=12.3, 4.7, 4.1 Hz, 1H), 1.04 (d, J=6.9 Hz, 3H), 0.39 (s, 3H), 0.38 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 149.2 (dddt, J=241.4, 17.4, 8.7, 4.0 Hz), 142.5, 142.0 (dtt, J=254.3, 12.9, 5.7 Hz), 138.3-136.2 (m), 128.5, 125.9, 110.0-109.3 (m), 34.9, 33.6, 19.0, 13.8, 3.34 (dt, J=14.4, 3.7 Hz), .sup.19F NMR (565 MHz, CD.sub.2Cl.sub.2) 126.48-126.61 (m), 152.97 (t, J=19.8 Hz), 162.37 (td, J=22.6, 8.6 Hz), .sup.29Si NMR (119 MHz, CDCl.sub.3) 4.07, FTIR (cm.sup.1): 3028, 2955, 2868, 1642, 1517, 1457, 1374, 1283, 1256, 1086, 969, 841, 802, 747, 699. HRMS (CI) m/z, calculated for [C.sub.17H.sub.16F.sub.5Si].sup.+: 343.0941; found: 343.0945.

Example 39Synthesis of Compound (40)

[0213] ##STR00089##

[0214] According to procedure B, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Et.sub.2O (1.3 mL), 4-biphenyldimethylsilyl chloride (300 mg, 1.2 mmol), and [1.43 M] (4-phenylbutan-2-yl)magnesium bromide (700 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitle:water=80:20 to acetonitrile:water=90:10) to afford compound (40) as a clear oil (287 mg, 83%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.64-7.61 (m, 2H), 7.61-7.55 (m, 4H), 7.45 (t, J=7.6 Hz, 2H), 7.36 (t, J=7.3 Hz, 1H), 7.25 (t, J=7.5 Hz, 2H), 7.14 (t, J=6.3 Hz, 3H), 2.84-2.76 (m, 1H), 2.53-2.44 (m, 1H), 1.87-1.78 (m, 1H), 1.48-1.39 (m, 1H), 1.06 (t, J=5.9 Hz, 3H), 1.00-0.92 (m, 1H), 0.31-0.27 (m, 6H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.0, 141.7, 141.3, 137.4, 134.6, 128.9, 128.6, 128.4, 127.5, 127.3, 126.5, 125.7, 35.0, 33.9, 19.0, 14.2, 4.5, 4.7, .sup.29Si NMR (119 MHz, CDCl.sub.3) 0.04, FTIR (cm.sup.1): 3062, 3025, 2952, 2863, 1597, 1496, 1485, 1454, 1384, 1250, 1115, 1007, 826, 811, 756, 697. HRMS (CI) m/z, calculated for [C.sub.23H.sub.25Si].sup.+: 329.1726; found: 329.1731.

Example 40Synthesis of Compound (41)

[0215] ##STR00090##

[0216] According to procedure B, (DrewPhos).sub.2PdI.sub.2(16 mg, 10 mol), Et.sub.2O (1.0 mL), 3-phenoxydimethylsilyl chloride (285 L, 1.2 mmol), and [1.43 M] (4-phenylbutan-2-yl)magnesium bromide (700 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) then reverse phase chromatography on C.sub.18 modified silica (gradient from acetonitle:water=80:20 to acetonitrile:water=90:10) to afford compound (41) as a clear oil (314 mg, 87%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.32 (q, J=7.5 Hz, 3H), 7.26-7.22 (m, 3H), 7.18-7.13 (m, 2H), 7.11 (d, J=7.1 Hz, 2H), 7.09 (t, J=7.4 Hz, 1H), 7.00-6.95 (m, 3H), 2.76 (ddd, J=14.9, 10.4, 4.9 Hz, 1H), 2.46 (ddd, J=13.5, 10.2, 6.6 Hz, 1H), 1.78 (dddd, J=13.8, 10.3, 6.6, 3.6 Hz, 1H), 1.40 (dtd, J=13.6, 10.2, 4.9 Hz, 1H), 1.02 (d, J=7.3 Hz, 3H), 0.96-0.87 (m, 1H), 0.25 (s, 3H), 0.24 (s, 3H), .sup.13C NMR (151 MHz, CD.sub.2Cl.sub.2) 158.2, 157.0, 143.5, 141.7, 130.3, 129.7, 129.6, 128.9, 128.8, 126.1, 125.1, 123.5, 120.0, 118.9, 35.4, 34.4, 19.4, 14.3, 4.5, 4.8, .sup.29Si NMR (119 MHz, CDCl.sub.3) 0.34, FTIR (cm.sup.1): 3061, 3026, 2952, 2864, 1566, 1489, 1476, 1401, 1226, 1110, 812, 771, 697. HRMS (CI) m/z, calculated for [C.sub.23H.sub.25SiO].sup.+: 345.1675; found: 345.1685.

Example 41Synthesis of Compound (42)

[0217] ##STR00091##

[0218] According to procedure C, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Bu.sub.2O (910 L), triethylsilyl chloride (340 L, 2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (42) as a clear oil (249 mg, 99%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.28 (t, J=7.6 Hz, 2H), 7.20-7.15 (m, 3H), 2.84 (ddd, J=14.1, 10.5, 4.8 Hz, 1H), 2.48 (ddd, J=13.5, 10.2, 6.7 Hz, 1H), 1.80 (dddd, J=13.6, 10.0, 6.6, 3.1 Hz, 1H), 1.50-1.41 (m, 1H), 1.04 (d, J=7.4 Hz, 3H), 0.93 (t, J=8.0 Hz, 9H), 0.81 (dqd, J=10.6, 7.4, 3.3 Hz, 1H), 0.54 (q, J=8.0 Hz, 6H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.2, 128.6, 128.4, 125.7, 35.3, 34.3, 16.7, 14.3, 7.8, 2.3, .sup.29Si NMR (119 MHz, CDCl.sub.3) 8.21, FTIR (cm.sup.1): 3027, 2952, 2909, 2874, 1604, 1496, 1454, 1416, 1238, 1016, 730, 698. HRMS (CI) m/z, calculated for [C.sub.16H.sub.27Si].sup.+: 247.1882; found: 247.1884.

Example 42Synthesis of Compound (43)

[0219] ##STR00092##

[0220] According to procedure C, (DrewPhos).sub.2PdI.sub.2 16 mg, 10 mol), Bu.sub.2O (880 L), cyclohexyldimethylsilyl chloride (370 L, 2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (43) as a clear oil (210 mg, 90%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.28 (t, J=7.6 Hz, 2H), 7.20-7.15 (m, 3H), 2.82 (ddd, J=14.3, 10.5, 4.8 Hz, 1H), 2.48 (ddd, J=13.5, 10.2, 6.7 Hz, 1H), 1.78 (dddd, J=13.6, 10.1, 6.6, 3.2 Hz, 1H), 1.74-1.67 (m, 3H), 1.61 (dd, J=26.0, 13.0 Hz, 2H), 1.46-1.36 (m, 1H), 1.24-1.15 (m, 3H), 1.13-1.03 (m, 2H), 1.01 (d, J=7.4 Hz, 3H), 0.74 (dqd, J=10.7, 7.4, 3.3 Hz, 1H), 0.68 (tt, J=12.7, 3.0 Hz, 1H), 0.11 (s, 3H), 0.12 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.3, 128.6, 128.4, 125.7, 35.2, 34.2, 28.37, 28.36, 27.9, 27.8, 27.2, 24.3, 17.2, 14.2, 6.9, .sup.29Si NMR (119 MHz, CDCl.sub.3) 5.66, FTIR (cm.sup.1): 3026, 2919, 2847, 1604, 1496, 1446, 1246, 1099, 996, 888, 833, 799, 767, 698. HRMS (CI) m/z, calculated for [C.sub.18H.sub.29Si].sup.+: 273.2039; found: 273.2031.

Example 43Synthesis of Compound (44)

[0221] ##STR00093##

[0222] According to procedure C, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Bu.sub.2O (950 L), isopropyldimethylsilyl chloride (310 L, 2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (44) as a clear oil (210 mg, 90%): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.28 (t, J=7.6 Hz, 2H), 7.20-7.15 (m, 3H), 2.83 (ddd, J=14.8, 10.6, 4.8 Hz, 1H), 2.49 (ddd, J=13.5, 10.3, 6.6 Hz, 1H), 1.78 (dddd, J=13.7, 10.1, 6.6, 3.2 Hz, 1H), 1.41 (ddt, J=14.0, 10.5, 5.3 Hz, 1H), 1.02 (d, J=7.4 Hz, 3H), 0.95-0.90 (m, 6H), 0.88-0.81 (m, 1H), 0.76 (dqd, J=10.7, 7.4, 3.3 Hz, 1H), 0.10 (s, 3H), 0.11 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.2, 128.6, 128.4, 125.7, 35.2, 34.3, 18.0, 17.9, 17.5, 14.2, 12.1, 7.20, 7.23, FTIR (cm.sup.1): 3027, 2953, 2864, 1604, 1496, 1454, 1249, 997, 883, 832, 808, 765, 697. HRMS (CI) m/z, calculated for [C.sub.14H.sub.23Si].sup.+: 219.1569; found: 219.1559.

Example 44Synthesis of Compound (45)

[0223] ##STR00094##

[0224] According to procedure C, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Bu.sub.2O (850 L), diphenylmethylsilyl chloride (410 L, 2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at RT for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (45) as a clear oil (315 mg, 95%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.50-7.47 (m, 4H), 7.39-7.31 (m, 6H), 7.24 (t, J=7.5 Hz, 2H), 7.16 (t, J=7.4 Hz, 1H), 7.10 (d, J=7.1 Hz, 2H), 2.80 (ddd, J=14.1, 9.9, 4.8 Hz, 1H), 2.50 (ddd, J=13.5, 9.5, 7.2 Hz, 1H), 1.91-1.82 (m, 1H), 1.51-1.43 (m, 1H), 1.41-1.33 (m, 1H), 1.09 (d, J=7.3 Hz, 3H), 0.53 (s, 3H), .sup.13C NMR (151 MHz, CD.sub.2Cl.sub.2) 143.4, 137.4, 137.2, 135.40, 135.37, 129.7, 129.6, 129.1, 128.8, 128.37, 128.35, 126.2, 35.4, 34.5, 17.8, 14.5, 6.2, .sup.29Si NMR (119 MHz, CDCl.sub.3) 4.7, FTIR (cm.sup.1): 3068, 2953, 2856, 1603, 1495, 1427, 1251, 1110, 788, 737, 698, 476. HRMS (CI) m/z, calculated for [C.sub.22H.sub.23Si].sup.+: 315.1569; found: 315.1579.

Example 45Synthesis of Compound (46)

[0225] ##STR00095##

[0226] According to procedure D, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Bu.sub.2O (1.25 mL), triphenylsilyl chloride (590 mg, 2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at 50 C. for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes:DCM 100:0 to hexanes:DCM 90:10) to afford compound (46) as a viscous clear oil (267 mg, 68%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.50 (dd, J=8.0, 1.4 Hz, 6H), 7.42-7.37 (m, 3H), 7.37-7.31 (m, 6H), 7.26 (t, J=7.5 Hz, 2H), 7.17 (t, J=7.4 Hz, 1H), 7.12 (d, J=7.0 Hz, 2H), 2.86 (ddd, J=13.8, 9.3, 4.7 Hz, 1H), 2.57 (dt, J=13.5, 8.3 Hz, 1H), 2.09-2.02 (m, 1H), 1.75-1.68 (m, 1H), 1.52-1.44 (m, 1H), 1.21 (d, J=7.3 Hz, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.2, 136.5, 135.2, 129.9, 129.2, 128.8, 128.4, 126.3, 35.3, 34.7, 16.7, 14.8, .sup.29Si NMR (119 MHz, CD.sub.2Cl.sub.2) 6-8.7, FTIR (cm-1): 3067, 3024, 2935, 2856, 1602, 1495, 1428, 1189, 1108, 998, 741, 698, 575, 510. HRMS (CI) m/z, calculated for [C.sub.22H.sub.23Si].sup.+: 315.1569; found: 315.1578.

Example 46Synthesis of Compound (47)

[0227] ##STR00096##

[0228] According to procedure D, (DrewPhos).sub.2PdI.sub.2 (16 mg, 10 mol), Bu.sub.2O (1.25 mL), tert-butyldimethylsilyl chloride (300 mg, 2 mmol), and [1.34 M] (4-phenylbutan-2-yl)magnesium bromide (750 L, 1.0 mmol) were combined under N.sub.2 and stirred at 100 C. for 24 h. After workup, crude product was purified via silica gel flash chromatography (hexanes) to afford compound (47) as a clear oil (74 mg, 30%): .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2) 7.26 (t, J=7.6 Hz, 2H), 7.20-7.14 (m, 3H), 2.83 (ddd, J=13.7, 10.5, 4.8 Hz, 1H), 2.48 (ddd, J=13.4, 10.2, 6.6 Hz, 1H), 1.85 (dddd, J=13.5, 10.2, 6.6, 2.9 Hz, 1H), 1.48-1.39 (m, 1H), 1.07 (d, J=7.4 Hz, 3H), 0.89 (s, 9H), 0.85 (ddq, J=15.0, 7.5, 4.5, 3.6 Hz, 1H), 0.070 (s, 3H), 0.075 (s, 3H), .sup.13C NMR (151 MHz, CDCl.sub.3) 143.2, 128.6, 128.4, 125.7, 35.2, 35.0, 27.6, 17.6, 17.4, 15.2, 7.0, .sup.29Si NMR (119 MHz, CDCl.sub.3) 9.7, FTIR (cm.sup.1): 3027, 2928, 2856, 1604, 1470, 1250, 828, 765, 697. HRMS (CI) m/z, calculated for [C.sub.15H.sub.25Si].sup.+: 233.1726; found: 233.1722.

All-Chloride Experiments

Synthesis of (DrewPhos).SUB.2.PdI.SUB.2

[0229] ##STR00097##

[0230] A 100 mL round bottom flask equipped with a magnetic stirbar was charged with bis(acetonitrile)dichloropalladium(II) (259 mg, 1 mmol, 1.0 equiv.) and DrewPhos (1.2 g, 2 mmol, 2.0 equiv.). The flask was sealed with a rubber septum and purged 10 min with N.sub.2. CH.sub.2Cl.sub.2 (20 mL) was added via syringe and the solution was stirred for 6 hours at RT. The solvent was then removed in vacuo. EtOAc (15 mL) was added and the flask sat overnight at RT. The solid was collected via vacuum filtration and rinsing with EtOH resulted in a stable, yellow solid (905 mg, 66% yield): .sup.1H NMR (600 MHz, CDCl.sub.3) 7.52-7.48 (m, 12H), 7.38 (s, 6H), 1.19 (s, 108H); .sup.13C NMR (151 MHz, CDCl.sub.3) 149.69 (t, J=5.0 Hz), 130.41 (t, J=23.9 Hz), 129.87 (t, J=6.4 Hz), 123.83, 35.01, 31.54, .sup.31P NMR (243 MHz, CDCl.sub.3) 26.82; FTIR (cm.sup.1): 2963, 2903, 2868, 1590, 1477, 1421, 1363, 1266, 1249, 1138, 731, 705, 586; mp=>250 C. HRMS (LIFDI) m/z, calculated for [C.sub.84H.sub.126P.sub.2PdCl.sub.2].sup.+: 1372.7747; found: 1372.7599.

Synthesis of Isopropylmagnesium Chloride

[0231] ##STR00098##

[0232] An oven-dried 25 mL round-bottom flask equipped with a magnetic stirbar and rubber septum was attached to a double manifold and cooled under vacuum. The flask was backfilled with N.sub.2, the septum removed, magnesium turnings (1.1 g, 45 mmol, 1.5 equiv.) were added. The septum was replaced; the flask was attached to a double manifold and purged with N.sub.2 for 10 min. The flask was held under positive N.sub.2 then Et.sub.2O (10 mL, [3 M]) was added. An initial amount of alkyl halide (200-400 L) was added and the reaction to start the reaction as evidenced by a minor exotherm. If reaction does not initiate, gentle warming (for example with a heating mantle) may be necessary. Once initiated, the flask was placed in a RT water bath and the remaining alkyl halide (2.74 mL, 2.36 g, 30 mmol, 1 equiv., total addition amount) was added dropwise over 30 min. After full addition of the alkyl halide, the mixture was allowed to stir at RT for an additional 4 h. The excess magnesium was allowed to settle and the mixture was filtered via cannula to a Schlenk tube. Titration resulted in a [2.65 M] solution of isopropylmagnesium chloride. In this preparation, 12 was not used to activate the magnesium turnings.

[0233] All-Chloride Process According to the Present Invention

[0234] In a nitrogen filled glovebox, a 1-dram vial equipped with a magnetic stirbar was charged with (DrewPhos).sub.2PdCl.sub.2 (3.4 mg, 2.5 mol, 0.01 equiv.), Et.sub.2O (350 L) or Bu.sub.2O (350 L), and dimethylphenylsilyl chloride (50 L, 51 mg, 300 mol, 1.2 equiv.). Vial was then sealed with a septum cap and removed from the glovebox. Isopropylmagnesium chloride [2.65 M] (94 L, 250 mol, 1 equiv.) was then added via syringe and the vial was then stirred at the indicated temperature for 24 h. The reaction was quenched with Et.sub.2O (1 mL) then H.sub.2O (0.5 mL) via syringe. n-Nonane (32 mg, 45 L, 0.25 mmol, 1 equiv.) and 1,3,5-trimethoxybenzene (TMB) (14 mg, 0.25 mmol, 0.33 equiv.) were added as GC internal standards. Brine (1 mL) and Et.sub.2O (1 mL) were then added and the vials shaken. An aliquot was then filtered through a MgSO.sub.4 and silica plug. The solution was directly analyzed by GC.

TABLE-US-00001 TABLE 1 All-Chloride Conditions [00099] [00100] Entry Solvent Temp Additive Yield (%).sup.a 1 Et.sub.2O rt 6 2 Bu.sub.2O 50 C. 70 3 Et.sub.2O rt 0.25 equiv TMEDA 52 .sup.aYields determined by GC. All reactions gave >99:1 B:L selectivity by GC.

[0235] All reactions in the following paragraphs were performed at 0.25 mmol in a nitrogen-filled glovebox with a [0.5 M] overall concentration based on the sum of all liquid reagents.

[0236] Examination of Stoichiometry

[0237] In a nitrogen filled glovebox, a 1-dram vial equipped with a magnetic stirbar was charged with (DrewPhos).sub.2PdI.sub.2 (4 mg, 2.5 mol, 0.01 equiv.), Et.sub.2O (330 L), and dimethylphenylsilyl chloride (52 L, 53 mg, 313 mol, 1.25 equiv., or 46 L, 47 mg, 275 mol, 1.1 equiv., or 42 L, 43 mg, 250 mol, 1 equiv.). Vial was then sealed with a septum cap and removed from the glovebox. Isopropylmagnesium bromide [2.13 M](117 L, 250 mol, 1 equiv., or 129 L, 275 L, 1.1 equiv., or 147 L, 313 mol, 1.25 equiv.) was then added via syringe and the vial was then stirred at RT for the indicated time. The reaction was quenched with Et.sub.2O (1 mL) then H.sub.2O (0.5 mL) via syringe. n-Nonane (32 mg, 45 L, 0.25 mmol, 1 equiv.) and 1,3,5-trimethoxybenzene (TMB) (14 mg, 0.25 mmol, 0.33 equiv.) were added as GC internal standards. Brine (1 mL) and Et.sub.2O (1 mL) were then added and the vials shaken. An aliquot was then filtered through a MgSO.sub.4 and Silica plug. The solution was directly analyzed by GC.

TABLE-US-00002 TABLE 2 Effect of Stoichiometry [00101] Entry Mg:Si 4 h (%).sup.a 8 h (%).sup.a 24 h (%).sup.a 1 1:1.25 99 99 99 2 1:1.1 78 96 99 3 1:1 73 90 97 4 1.1:1 74 88 93 5 1.25:1 71 86 93 .sup.aYields determined by GC. All reactions gave >99:1 B:L selectivity by GC.

[0238] Examination of Ethereal Solvents

[0239] In a nitrogen filled glovebox, a 1-dram vial equipped with a magnetic stirbar was charged with (DrewPhos).sub.2PdI.sub.2 (4 mg, 2.5 mol, 0.01 equiv.), MTBE or CPME (280 L), and triethylsilyl chloride (84 L, 75 mg, 500 mol, 2 equiv.) or isopropyldimethylsilyl chloride (78 L, 68 mg, 500 mol, 2 equiv.). Vial was then sealed with a septum cap and removed from the glovebox. (4-phenylbutan-2-yl)magnesium bromide [1.78 M] (140 L, 250 mol, 1 equiv.) was then added via syringe and the vial was then stirred at 50 C. for the indicated time. The reaction was quenched with Et.sub.2O (1 mL) then H.sub.2O (0.5 mL) via syringe. n-Nonane (32 mg, 45 L, 0.25 mmol, 1 equiv.) and 1,3,5-trimethoxybenzene (TMB) (14 mg, 0.25 mmol, 0.33 equiv.) were added as GC and NMR internal standards. Brine (1 mL) and Et.sub.2O (1 mL) were then added and the vials shaken. An aliquot was then filtered through a MgSO.sub.4 and Silica plug. The solution was directly analyzed by GC then concentrated in vacuo and analyzed by NMR.

TABLE-US-00003 TABLE 3 Examination of Ethereal Solvents [00102] [00103] Entry [Si] MTBE CPME 1 Et.sub.3Si 99 99 2 .sup.iPrMe.sub.2Si 97 90 .sup.aYields determined by NMR. All reactions gave >99:1 B:L selectivity by GC.

[0240] Examination of Silyl Electrophiles

[0241] The use of other silyl electrophiles other than silyl iodides was also examined. Previous studies have shown that the addition of iodide additives can be beneficial with use of silyl chlorides, bromides, and triflates, so the reaction was also examined with NaI additive. The results show minimal reactivity with Me.sub.3SiBr in the absence of NaI, and modest reactivity with. For silyl chlorides and triflates, negligible reactivity was observed with or without NaI.

[0242] In a nitrogen filled glovebox, a 1-dram vial equipped with a magnetic stirbar was charged with (DrewPhos).sub.2PdI.sub.2 (0.01 equiv.), dioxane, triethylamine (1 equiv.), and trimethylsilyl halide (2 equiv.). Vial was then sealed with a septum cap and removed from GB. (4-phenylbutan-2-yl)zinc bromide (1 equiv.) was added via syringe and the flask was then stirred at RT for 4 h. The reaction was quenched with Et.sub.2O (1 mL) then H.sub.2O (0.5 mL) via syringe. Nonane (32 mg, 45 L, 0.25 mmol, 1 equiv.) and 1,3,5-trimethoxybenzene (TMB) (14 mg, 0.25 mmol, 0.33 equiv.) were added as GC and NMR internal standards respectively. Brine (1 mL) and Et.sub.2O (1 mL) were then added and the vials shaken. An aliquot was then filtered through a MgSO.sub.4 and Silica plug. The solution was directly analyzed by GC. The solvent was removed in vacuo then analyzed by NMR.

TABLE-US-00004 TABLE 4 Examination of Silyl Electrophiles [00104] [00105] Entry Me.sub.3SiX 0 equiv NaI.sup.a 3 equiv NaI.sup.a 1 Me.sub.3SiI 98% 99% 2 Me.sub.3SiBr 26% 61% 3 Me.sub.3SiCl 1% 11% 4 Me.sub.3SiOTf 2% 5% .sup.aYields obtained by .sup.1H NMR with TMB as an internal standard.

[0243] Examination of Dibutyl Zinc Reactivity

[0244] The use of dialkylzinc reagents in the coupling reaction was also examined. As can be seen in Table 5, with Bu.sub.2Zn only trace background reaction is observed, which is comparable to the background reaction with BuZnBr. Under palladium-catalyzed conditions, quantitative alkylation resulted. Et.sub.3N does not effect this reaction. It is notable that only 0.5 equiv of Bu.sub.2Zn is required in this reaction, both alkyl groups transfer to the product.

[0245] In a nitrogen filled glovebox, a 1-dram vial equipped with a magnetic stirbar was charged with (DrewPhos).sub.2PdI.sub.2 (0.01 equiv.), dioxane, triethylamine (1 equiv.), and dimethylphenylsilyl iodide (2 equiv.), and dibutylzinc (0.5 equiv.). Vial was then sealed with a septum cap, removed from GB, and stirred at RT for 4 h. The reaction was quenched with Et.sub.2O (1 mL) then H.sub.2O (0.5 mL) via syringe. Nonane (32 mg, 45 L, 0.25 mmol, 1 equiv.) and 1,3,5-trimethoxybenzene (TMB) (14 mg, 0.25 mmol, 0.33 equiv.) were added as GC and NMR internal standards respectively. Brine (1 mL) and Et.sub.2O (1 mL) were then added and the vials shaken. An aliquot was then filtered through a MgSO.sub.4 and Silica plug. The solution was directly analyzed by GC. The solvent was removed in vacuo then analyzed by NMR.

TABLE-US-00005 TABLE 5 Reactivity of Dibutylzinc [00106] [00107] Entry % Pd 1 equiv Et.sub.3N.sup.a 0 equiv Et.sub.3N.sup.a 1 1 99% 99% 2 0 7% 7% .sup.aYields obtained by .sup.1H NMR with TMB as an internal standard.

[0246] Isolation of the palladium catalyzed reaction in the presence of triethylamine via flash chromatography (hexanes) afforded 5 as a clear oil (42 mg, 88%): .sup.1H NMR (400 MHz, CDCl.sub.3) 7.54-7.50 (m, 2H), 7.37-7.34 (m, 3H), 1.36-1.26 (m, 4H), 0.88 (t, J=6.9 Hz, 3H), 0.79-0.73 (m, 2H), 0.26 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 139.9, 133.7, 128.9, 127.8, 26.7, 26.3, 15.6, 13.9, 2.9.

[0247] Examination of Alkene Additives

[0248] Alkenes appear to interfere with the reaction, as is reflected in the study shown in Table 6. This appears to be a function of alkene substitution, as the effect is most notable with lower substituted alkenes.

[0249] In a nitrogen filled glovebox, a 1-dram vial equipped with a magnetic stirbar was charged with (DrewPhos).sub.2PdI.sub.2 (0.01 equiv), dioxane, triethylamine (1 equiv), alkene (1 equiv) and trimethylsilyl halide (2 equiv). Vial was then sealed with a septum cap and removed from GB. Isopropylzinc bromide (1 equiv) was added via syringe and the flask was then stirred at RT for 4 h. The reaction was quenched with Et.sub.2O (1 mL) then H.sub.2O (0.5 mL) via syringe. Nonane (32 mg, 45 L, 0.25 mmol, 1 equiv) and 1,3,5-trimethoxybenzene (TMB) (14 mg, 0.25 mmol, 0.33 equiv) were added as GC and NMR internal standards respectively. Brine (1 mL) and Et.sub.2O (1 mL) were then added and the vials shaken. An aliquot was then filtered through a MgSO.sub.4 and Silica plug. The solution was directly analyzed by GC. The solvent was removed in vacuo then analyzed by NMR.

TABLE-US-00006 TABLE 6 Impact of Alkene Additives [00108] [00109] Entry Alkene 1 + 2%.sup.a 1:2.sup.b 1 None 98 >99:1 2 4-octene 55 98:2 3 1-methyl- 99 >99:1 cyclohexene 4 (+)-limonene 75 >99:1 .sup.aYields obtained by .sup.1H NMR with TMB as an internal standard. .sup.bRatio determined by GC.