ORGANOMETALLIC COMPOUNDS

Abstract

The invention relates to new processes for preparing palladium complexes, allowing preparation of known products with high purity and in good yields and also allowing preparation of new palladium complexes. The invention also relates to new palladium complexes that are suitable as precatalysts and/or catalysts, in particular for coupling reactions.

Claims

1.-43. (canceled)

44. A method for preparing a compound according to general formula
[PdZ.sup.AZ.sup.B](I) wherein the phosphine ligands Z.sup.A and Z.sup.B are independently selected from the group consisting of tri-tert-butylphosphine (PtBu.sub.3), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu.sub.2), tert-butyl-di-(isopropyl)phosphine (P(iPr).sub.2tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu.sub.2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad).sub.2tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr.sub.2), di(1-adamantyl)isopropylphosphine (P(1-Ad).sub.2iPr), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp), comprising the steps of: A. providing i. a mononuclear or multinuclear palladium compound, wherein at least one palladium center bears a ligand L.sub.S, which is an organosilicon compound, and ii. in each case one phosphine ligand Z.sup.A and Z.sup.B, wherein Z.sup.A and Z.sup.B are independently selected from the group consisting of tri-tert-butylphosphine (PtBu.sub.3), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu.sub.2), tert-butyl-di-(isopropyl)phosphine (P(iPr).sub.2tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu.sub.2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad).sub.2tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr.sub.2), di(1-adamantyl)isopropylphosphine (P(1-Ad).sub.2iPr), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp), B. reacting the palladium compound and the monophosphine ligand and/or the bisphosphine ligand from step A. in a non-ethereal solvent S.sub.C and C. optionally isolating the compound according to general formula [PdZ.sup.AZ.sup.B] (I) prepared in step B.

45. A compound according to general formula [PdZ.sup.AZ.sup.B] (I) obtained by the method according to claim 44, wherein the compound is of formula (I.1) ##STR00157##

46. A compound according to general formula [PdZ.sup.AZ.sup.B] (I), wherein the compound is [Pd(PtBu.sub.3)(P(1-Ad)tBu.sub.2)], [Pd(PtBu.sub.3)(P(1-Ad)iPr.sub.2)], [Pd(P(1-Ad).sub.2tBu).sub.2], [Pd(P(1-Ad).sub.2iPr).sub.2], [Pd(P(1-Ad)tBu.sub.2)(P(1-Ad)iPr.sub.2)], [Pd(P(1-Ad)iPr.sub.2).sub.2], [Pd(P(iPr).sub.2tBu).sub.2], [Pd(dppe).sub.2] or [Pd(dppp).sub.2].

47. A preparation containing i. a compound according to general formula [PdZ.sup.AZ.sup.B] (I), wherein Z.sup.A and Z.sup.B are independently selected from the group consisting of tri-tert-butylphosphine (PtBu.sub.3), di-tert-butyl(iso-propyl)phosphine (P(iPr)tBu.sub.2), tert-butyl-di-(isopropyl)phosphine (P(iPr).sub.2tBu), 1-adamantyl-di-(tert-butyl)phosphine (P(1-Ad)tBu.sub.2), di(1-adamantyl)-tert-butylphosphine (P(1-Ad).sub.2tBu), 1-adamantyl-di-(isopropyl)phosphine (P(1-Ad)iPr.sub.2), di(1-adamantyl)isopropylphosphine (P(1-Ad).sub.2iPr), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphosphino)propane (dppp), and ii. an organosilicon compound.

Description

EXEMPLARY EMBODIMENTS

[0674] A. Pd(0) complexes [Pd(phosphine).sub.2] and [Pd(dvds)(phosphine)]

[0675] Here, dvds=1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

Examples 1: Preparation of Pd Complexes

[0676] ##STR00073##

TABLE-US-00004 TABLE B-0 Other complexes and type of compounds obtained No. Ligand (L) Type A Type B 1 P.sup.tBu.sub.3 ? x 2 PCy.sub.3 x ? 3 P.sup.iPr.sub.3 x ? 4 PAd.sub.2Bu x ? 5 CyJohnPhos x ? 6 YPhos1 x ? (Cy.sub.2PCH.sub.2MePCy.sub.3)* 7 P.sup.tBu.sub.2Ph x ? 8 P.sup.tBu.sub.2.sup.iPr x ? 9 P.sup.tBuPh.sub.2 x ? 10 P(o-Tol).sub.3 x ? 11 P(C.sub.6F.sub.5).sub.3 x ? *Comparative example

General Procedure:

[0677] 422 ?l (434 mg, 0.5 mmol, 1 eq.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium (Pd-VS, or palladium-VS) were initially charged in an inertized Schlenk tube (heated three times with evacuation and loaded with argon), followed by 2 equivalents (1 mmol) of the corresponding phosphine, dissolved in a sufficient amount (usually approx. 3-4 ml) of toluene (unless otherwise stated). After the specified reaction time at room temperature, the volume was reduced to half, the precipitate formed was filtered off and washed with 3?2 ml methanol and dried under vacuum.

Example 1-1

[0678] Ligand: Tri-tert-butylphosphine, 2 ml ethanol as solvent. [0679] Reaction time: 4 h [0680] Yield: 92% colorless solid.

[0681] .sup.1H NMR (250 MHz, C.sub.6D.sub.6) ?=1.52 (t, J=5.5 Hz, 54H) ppm.

[0682] .sup.13C NMR (63 MHz, C.sub.6D.sub.6) ?=37.9, 33.7 ppm.

[0683] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=85.14 (s) ppm.

[0684] Silicon content by means of ICP-AES=340 ppm.

Example 1-2

[0685] Ligand: Tricyclohexylphosphine [0686] Reaction time: 3 h, then addition of 3 ml of methanol [0687] Yield: 163 mg (54%) colorless solid.

[0688] .sup.1H NMR (250 MHz, C.sub.6D.sub.6) ?=3.43-3.69 (m, 2H), 3.12-3.42 (m, 4H), 1.92-2.14 (m, 3H), 1.51-1.92 (m, 16H), 0.94-1.48 (m, 15H), 0.58 (s, 6H), 0.07 (s, 6H) ppm.

[0689] .sup.13C NMR (63 MHz, C.sub.6D.sub.6) ?=64.4, 63.2, 37.0, 31.3, 28.4, 27.4, 2.4, ?0.3 ppm. .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=34.85 (s) ppm.

Example 1-3

[0690] Ligand: Triisopropylphosphine (1.2 equivalents) [0691] Reaction time: 16 h. [0692] Yield: 246 mg (51%) colorless solid

[0693] .sup.1H NMR (250 MHz, C.sub.6D.sub.6) ?=3.48-3.60 (m, 2H), 3.18-3.29 (m, 4H), 1.96 (spt, J=14.4 Hz, 3H), 0.99 (dd, J=13.0, 7.1 Hz, 18H), 0.56 (s, 6H), 0.04 (s, 6H) ppm.

[0694] .sup.13C NMR (63 MHz, C.sub.6D.sub.6) ?=64.3, 63.0, 26.8, 20.5, 2.4, ?0.2 ppm.

[0695] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=47.79 (s) ppm.

Example 1-4

[0696] Ligand: Butyldi-1-adamantylphosphine [0697] Reaction time: 3 h, toluene [0698] Yield: 193 mg (55%) colorless solid; with acetone as solvent >80%.

[0699] .sup.1H NMR (250 MHz, C.sub.6D.sub.6) ?=3.76 (ddd, J=12.2, 5.1, 1.7 Hz, 2H), 3.14-3.53 (m, 4H), 1.97-2.12 (m, 12H), 1.86 (br. s., 8H), 1.55-1.75 (m, 14H), 1.42-1.55 (m, 2H), 0.97 (t, J=7.2 Hz, 3H), 0.58 (br. s., 6H), ?0.12-0.31 (m, 6H) ppm.

[0700] .sup.13C NMR (63 MHz, C.sub.6D.sub.6) ?=64.5, 64.0, 41.1, 40.0, 37.6, 31.1, 29.6, 26.8, 21.9, 14.8, 0.9 ppm.

[0701] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=49.78 (s) ppm.

[0702] Observation: Reaction Product

##STR00074##

Example 1-5

[0703] Ligand: 2-(dicyclohexylphosphino)biphenyl [0704] Reaction time: 16 h, addition of 3 ml of methanol after the reaction time [0705] Yield: 91 mg (45%) colorless solid

[0706] .sup.1H NMR (250 MHz, C.sub.6D.sub.6) ?=7.57 (t, J=7.1 Hz, 1H), 7.17-7.24 (m, 6H because of overlap with solvent signal), 7.03-7.09 (m, 2H), 6.94-7.03 (m, 3H), 3.12-3.39 (m, 4H), 2.90-3.10 (m, 2H), 1.81-2.08 (m, 6H), 1.51-1.78 (m, 6H), 1.23-1.51 (m, 4H), 0.97-1.23 (m, 6H), 0.57 (br. s., 6H), 0.12 (br. s, 6H) ppm.

[0707] .sup.13C NMR (63 MHz, C.sub.6D.sub.6) ?=146.8, 142.3, 133.5, 132.6, 132.2, 129.3, 127.2, 127.1, 126.4, 65.2, 64.3, 39.1, 30.9, 30.7, 27.8, 27.5, 26.5, 1.7, ?1.2 ppm.

[0708] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=32.83 ppm.

Comparative Example 1-6

[0709] Ligand: YPhos 1 [0710] Reaction time: 3 h [0711] Yield: 45 mg (56%) colorless solid.

[0712] .sup.31P NMR (101 MHz, C.sub.6D.sub.6) ?=30.96 (d, J=78.0 Hz), 15.76 (d, J=79.0 Hz) ppm.

Example 1-7

[0713] Ligand: Di-tert-butylphenylphosphine [0714] Reaction time: 3 h; after concentration, addition of 15 ml of methanol [0715] Yield: 123 mg (48%) colorless solid.

[0716] .sup.1H NMR (250 MHz, C.sub.6D.sub.6) ?=7.52-7.69 (m, 2H), 7.05-7.14 (m, 3H), 3.65 (s, 2H), 3.27-3.46 (m, 4H), 1.20 (d, J=12.6 Hz, 18H), 0.19 (br. s., 12H) ppm.

[0717] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=69.85 ppm.

Example 1-8

[0718] Ligand: Di-tert-butylisopropylphosphine, addition of 6 ml of toluene [0719] Reaction time: 3 h; after concentration, addition of 15 ml of methanol [0720] Yield: 153 mg (64%) colorless solid.

[0721] .sup.1H NMR (250 MHz, C.sub.6D.sub.6) ?=3.45-3.68 (m, 2H), 3.14-3.39 (m, 4H), 2.42-2.70 (m, 1H), 1.05-1.37 (m, 24H), 0.53 (br. s., 6H), ?0.19-0.24 (br. s., 6H) ppm

[0722] .sup.13C NMR (63 MHz, C.sub.6D.sub.6) ?=66.2, 65.9, 37.2, 31.8, 31.0, 22.2, 1.8 ppm.

[0723] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=71.27 ppm.

Example 1-9

[0724] Ligand: tert-butyldiphenylphosphine, addition of 2 ml of toluene [0725] Reaction time: 3 h; after concentration, addition of 15 ml of methanol [0726] Yield: 110 mg (41%) colorless solid.

[0727] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=7.51-7.73 (m, 4H), 6.95-7.13 (m, 6H), 3.38-3.67 (m, 4H), 3.15-3.31 (m, 2H), 1.19 (d, J=13.6 Hz, 9H), 0.50 (s, 6H), 0.03 (s, 6H) ppm.

[0728] .sup.13C NMR (101 MHz, C.sub.6D.sub.6) ?=137.2 (d, J=21.60 Hz) 134.8 (d, J=13.30 Hz) 129.6 (s) 69.0 (d, J=3.32 Hz) 68.1 (d, J=8.29) 34.2 (d, J=9.90 Hz) 29.3 (d, J=8.29 Hz) 2.2 (s) ?0.4 (s) ppm.

[0729] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=64.01 ppm.

Example 1-10

[0730] Ligand: Tri-o-tolylphosphine, addition of 3 ml of toluene

[0731] 63 mg of tri-o-tolylphosphine (0.2 mmol, 2 eq.) were added to an oven-dried vial, followed by 95 ?l (98 mg, 0.1 mmol, 1 eq.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium. 3 ml of toluene were added to this suspension and the resulting solution was analyzed by means of .sup.31P{.sup.1H} NMR.

[0732] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=21.6 ppm.

Example 1-11

[0733] Ligand: Tris(pentafluorophenyl)phosphine, addition of 3 ml of toluene

[0734] 110 mg of tris(pentafluorophenyl)phosphine (0.2 mmol, 2 eq.) were added to an oven-dried vial, followed by 95 ?l (98 mg, 0.1 mmol, 1 eq.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium. 3 ml of toluene were added to this suspension and the resulting solution was analyzed by means of .sup.19F-NMR.

Example 2: Catalytic Activity of Example 1-4

[0735] In the following example, the catalytic activity of example 1-4 of the compound

##STR00075##

was tested. This was carried out partly in comparison to other similar compounds. The activity was tested in a Suzuki-Myaura cross-coupling with p-chlorotoluene and phenylboronic acid as reactants.

##STR00076## [0736] A: Example 1-5 [0737] B: Example 1-3 [0738] C: Example 1-2 [0739] D: Example 1-4

##STR00077##

TABLE-US-00005 TABLE 2-1 Comparison of catalysts A-D. Unreacted reactant Yield at 3 No. Catalyst 1 [%] [%] 1 A 41 61 2 B 37 31 3 C 34 43 4 D 23 79

[0740] Reactions performed on 1.5 mmol scale. 2 mmol of phenylboronic acid, 1.5 mmol of K3P04 and 1.5 mmol of potassium fluoride were initially charged in an injection vial, 0.0075 mmol of catalyst was added in a nitrogen-filled glove box. Solvent: 4 ml THF. 1.5 mmol of p-chlorotoluene were added with a syringe. The reaction time was 22 h, and the temperature was 100? C. Yields determined via gas chromatography with tetradecane as internal standard.

[0741] The solvent tolerance was carried out analogously to the procedure under 2-1, with 3 ml of the specified solvent.

TABLE-US-00006 TABLE 2-2 Solvent tolerance of catalyst D. Unreacted Yield of product No. Solvent reactant 1 [%] 3 [%] 1 THF 13 95 2 MeOH 53 40 3 EtOH 45 46 4 .sup.tAmylOH 0 94 5 Toluene 28 77 6 Water 0 94 7 Water/THF (1:1) 11 99 8 Acetone 17 64

[0742] Furthermore, different bases were tested in suitable solvents. 1 mmol of base was used in each case.

TABLE-US-00007 TABLE 2-3 Base screening with catalyst D. Unreacted Yield of No. Base Solvent reactant 1 [%] product 3 [%] 1 K.sub.3PO.sub.4 Water 8 >99 2 Cs.sub.2CO.sub.3 Water 8 >99 3 Li.sub.2CO.sub.3 Water 0 >99 4 K.sub.2CO.sub.3 Water 7 >99 5 Na.sub.2CO.sub.3 Water 7 98 6 NaOH Water 8 >99 7 KOH Water 0 >99 8 .sup.tBuOK THF 0 >99 9 .sup.tBuONa THF 0 >99 10 .sup.tBuOLi THF 15 85

[0743] The suitability of different reaction temperatures was tested analogously to 2-1. 3 mmol of lithium carbonate were used as the base, and THE was used as the solvent. At temperatures below 80? C. no reaction product was observed, at 80? C. the yield was only 25%.

Example 3-1 [Pd(Ph.SUB.2.P(CH.SUB.2.).SUB.3.PPh.SUB.2.).SUB.2.]

[0744] Under argon, 213 mg of 1,3-bis(diphenylphosphino)propane (0.5 mmol, 2 eq.) were dissolved in 3 ml of toluene and 251 ?l (244 mg, 0.25 mmol, 1 eq.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium were added. The solution was stirred for 2 h, whereupon a yellow solid precipitated. 5 ml of methanol were added to the suspension and the supernatant was removed with a syringe. The solid was washed with methanol (2?10 ml) and dried under vacuum. [0745] Yield: 230 mg (99%).

[0746] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=3.97 ppm.

Example 3-2 [Pd(Ph.SUB.2.P(CH.SUB.2.).SUB.2.PPh.SUB.2.).SUB.2.]

[0747] Under argon, 203 mg of 1,3-bis(diphenylphosphino)ethane (0.5 mmol, 2 eq.) were dissolved in 3 ml of toluene and 251 ?l (244 mg, 0.25 mmol, 1 eq.) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane-palladium were added. The solution was stirred for 2 h, whereupon a solid precipitated. 5 ml of methanol were added to the suspension and the supernatant was removed with a syringe. The solid was washed with methanol (2?10 ml) and dried under vacuum. [0748] Yield: 215 mg (95%).

[0749] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=29.59 ppm.

B. Pd(I) Dimers [Pd(?-X)(PR.sup.AR.sup.BR.sup.C)].sub.2, Wherein X?Br, I

Example 1-1 [Pd(?-Br)(PtBu.SUB.3.)].SUB.2 .Starting from [Pd(acac).SUB.2.] and acetyl bromide

[0750] A mixture of [Pd(acac).sub.2] (31 g, 100 mmol) and acetyl bromide (25 g, 200 mmol) in 500 ml of acetone was stirred at room temperature for 2.5 hours. Then [Pd(PtBu.sub.3).sub.2] (55 g, 105 mmol, 1.05 eq.) and 400 ml of acetone were added and the reaction mixture was stirred at room temperature for 2 hours. The precipitated solid was filtered off, washed and then dried under vacuum. [0751] Yield: 71.58 g (92%) dark green-blue solid.

[0752] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=1.32 ppm.

[0753] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=86.3 ppm. Pd content: 28.1%.

[0754] Reversing the order of addition of acetyl bromide and [Pd(PtBu.sub.3).sub.2] gives the product in a yield of approx. 60%.

Example 1-2 [Pd(?-Br)(PtBu.SUB.3.)].SUB.2 .Starting from [Pd.SUB.2.(dvds).SUB.3.] and Acetyl Bromide or N-Bromosuccinimide

[0755] A mixture of [Pd.sub.2(dvds).sub.3] and acetyl bromide (2 eq.) in methanol was stirred at room temperature for 2.5 hours. PtBu.sub.3 (2 eq.) was then added and stirring was carried out for 2.5 hours at room temperature. The precipitated solid was filtered off, washed and then dried under vacuum. [0756] Yield: 32% dark green-blue solid.

[0757] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=1.32 ppm.

[0758] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=86.3 ppm.

[0759] Using N-bromosuccinimide as the Br donor and acetone as the solvent, and otherwise carrying out the reaction analogously, gave the product in a yield of 16%.

Example 1-3 [Pd(?-Br)(PtBu.SUB.3.)].SUB.2 .Starting from [Pd.SUB.2.(dvds).SUB.3.] and Br.SUB.2 .in 1,4-Dioxane

[0760] [Pd.sub.2(dvds).sub.3] (868 mg, 1 mmol) was added to a Schlenk tube, followed by tri-tert-butylphosphine (413 mg, 2 mmol, 98%, 2 eq.). A solution of bromine (Br.sub.2) (4 ml, 0.25 M, 1 mmol, 1 eq.) in 1,4-dioxane was then added. The mixture was stirred for 2 h at 40? C. The solvent was removed under reduced pressure, the residue extracted with toluene, and the toluene removed under reduced pressure. The solid obtained was dissolved in acetone. The solution was stored at ?20? C., whereupon dark green crystals were obtained, which were separated from the solution and washed with small portions of acetone and dried under reduced pressure. [0761] Yield: 55% dark green crystals.

[0762] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=1.32 ppm.

[0763] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=86.3 ppm.

Example 2-1 [Pd(?-I)(PtBu.SUB.3.)].SUB.2 .Starting from [Pd.SUB.2.(dvds).SUB.3.] and 12

[0764] A mixture of [Pd.sub.2(dvds).sub.3] (0.5 g Pd, 2.4 mmol) and PtBu.sub.3 as a solution in toluene (1 eq.) in acetone was stirred at room temperature for 2.5 hours. Iodine (I.sub.2) (0.62 g, 2.4 mmol, 1 eq.) was then added and stirring was carried out for 2.5 hours at room temperature. The precipitated solid was filtered off, washed and then dried under vacuum. [0765] Yield: 83% dark purple solid.

[0766] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=1.29 ppm.

[0767] .sup.31P{.sup.1H} NMR (101 MHz, C.sub.6D.sub.6) ?=102.3 ppm.

C. ?-Allylpalladium Halide Complexes

C.1 General Procedure for Preparing Dimeric Allylpalladium Halides According to General Formula VIII

[0768] An allyl halide (1.2 equivalents, 0.6 mmol; or 5 equivalents, 2.5 mmol; or 10 equivalents, 5 mmol) was added to a solution of Pd(vs) in a Schlenk flask under an argon atmosphere. (1 equivalent, palladium content 5.35%, 993 mg, 0.5 mmol or palladium content 10.9%, 488 mg, 0.5 mmol). A yellow solid formed rapidly. The mixture continued to be stirred for one hour and hexane (3 ml) was added. The liquid supernatant was decanted and the solid washed twice with 3 ml of hexane. The solid was dried under vacuum.

Example 1-1: Di-?-chlorobis(?.SUP.3.-allyl)dipalladium (1-Cl) [CAS Number: 12012-95-2]

[0769] ##STR00078##

[0770] Yellow solid, melting point: 149? C. Proportion of insoluble components in dichloromethane: <0.1% (PTFE membrane filter (0.45 ?m pore width)).

TABLE-US-00008 Pd(vs) Palladium content 5.35%, Palladium content 10.9%, 993 mg, 0.5 mmol 488 mg, 0.5 mmol Allyl chloride 46.9 mg, 50 ?l, 0.6 mmol 46.9 mg, 50 ?l, 0.6 mmol Yield 91 mg, >99% 91 mg, >99%

[0771] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=5.46 (tt, J=12.1, 6.7 Hz, 2H), 4.12 (d, J=6.6 Hz, 4H), 3.05 (d, J=12.1 Hz, 4H).

[0772] .sup.13C NMR (CDCl.sub.3, 101 MHz) ?=111.1, 62.9.

Example 1-2: Di-?-bromobis(?.SUP.3.-allyl)dipalladium (1-Br) [CAS Number: 12077-82-6]

[0773] ##STR00079## [0774] Yellow solid, melting point: 158? C.

TABLE-US-00009 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol Allyl bromide 598 mg, 0.43 ml, 5 mmol Yield 113 mg, >99%

[0775] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=5.43 (tt, J=12.1, 6.8 Hz, 2H), 4.20 (d, J=6.8 Hz, 4H), 3.08 (d, J=12.1 Hz, 4H).

[0776] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=110.6, 64.8.

Example 1-3: Di-?-iodobis(?.SUP.3.-allyl)dipalladium (1-1) [CAS Number: 12013-04-6]

[0777] ##STR00080## [0778] Orange solid, melting point: 180? C.

TABLE-US-00010 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol Allyl iodide 860 mg, 0.47 ml, 5 mmol Yield 137 mg, >99%

[0779] .sup.1H NMR (CDCl.sub.3, 250 MHz): ?=5.31 (tt, J=12.5, 6.8 Hz, 2H), 4.39 (dt, J=6.8, 0.7 Hz, 4H), 3.09 (dt, J=12.5, 0.7 Hz, 4H).

[0780] .sup.13C NMR (CDCl.sub.3, 63 MHz): ?=109.5, 67.6.

Example 1-4: Di-?-chlorobis[?.SUP.3.-2-methylallyl]dipalladium (2-Cl) [CAS Number: 12081-18-4]

[0781] ##STR00081## [0782] Yellow solid, melting point: 145? C.

TABLE-US-00011 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol 3-chloro-2-methylpropene 503 mg, 0.54 ml, 5 mmol Yield 98 mg, >99%

[0783] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=3.86 (s, 4H), 2.89 (s, 4H), 2.15 (s, 6H).

[0784] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=127.0, 61.8, 22.7.

Example 1-5: Di-?-bromobis[?.SUP.3.-2-methylallyl]dipalladium (2-Br) [CAS Number: 12080-98-7]

[0785] ##STR00082## [0786] Yellow solid, melting point: 153-154? C.

TABLE-US-00012 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol 3-bromo-2-methylpropene 348 mg, 0.26 ml, 2.5 mmol Yield 111 mg, 92.0%

[0787] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=3.94 (s, 4H), 2.92 (s, 4H), 2.09 (s, 6H).

[0788] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=126.2, 63.9, 22.9.

Example 1-6: Bis[(1,2,3-?)-2-buten-1-yl]di-?-chlorodipalladium (3-Cl) [CAS Number: 12081-22-0]

[0789] ##STR00083## [0790] Yellow solid, melting point: 148? C.

TABLE-US-00013 Pd(vs) Palladium content 5.35%, Palladium content 10.9%, 993 mg, 0.5 mmol 9.76 g, 10 mmol Crotyl chloride 477 mg, 0.51 ml, 5 mmol 1.14 g, 1.23 ml, 12 mmol Yield 98 mg, >99% 1.84 mg, 93.5% Ratio of syn/anti isomers 97:3
SYN isomer:

[0791] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=5.30 (td, J=11.6, 6.7 Hz, 2H), 3.78-4.01 (m, 4H), 2.82 (d, J=11.9 Hz, 2H), 1.34 (d, J=6.3 Hz, 6H).

[0792] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=111.4, 79.0, 59.2, 15.8.

Anti Isomer:

[0793] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=4.86 (quin, J=6.8 Hz, 2H), 4.10 (d, J=7.3 Hz, 2H), 3.37 (d, J=12.9 Hz, 2H), 1.13 ppm (d, J=6.6 Hz, 6H) a proton overlaps with the syn isomer.

[0794] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=106.4, 81.5, 58.3, 18.0.

Example 1-7: Bis[(1,2,3-?)-2-buten-1-yl]di-?-chlorodipalladium (3-Br) [CAS Number: 12081-43-5]

[0795] ##STR00084## [0796] Yellow solid, melting point: 169? C.

TABLE-US-00014 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol Crotyl bromide Purity 85%, 394 mg, 0.30 ml, 2.48 mmol Yield 121 mg, >99%

[0797] .sup.1H NMR (CDCl.sub.3, 250 MHz): ?=5.29 (td, J=11.6, 6.8 Hz, 2H), 3.89-4.09 (m, 4H), 2.85 (d, J=12.0 Hz, 2H), 1.50 (d, J=6.3 Hz, 6H).

[0798] .sup.13C NMR (CDCl.sub.3, 63 MHz): ?=111.2, 83.8, 59.7, 18.5.

Example 1-8: Di-?-chlorobis[(1,2,3-?)-3-methyl-2-butenyl]dipalladium (4-Cl) [CAS Number: 12288-41-4]

[0799] ##STR00085## [0800] Yellow solid, melting point: 116-117? C.

TABLE-US-00015 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol 3,3-dimethylallyl chloride 278 mg, 0.30 ml, 2.5 mmol Yield 97 mg, 91.9%

[0801] .sup.1H NMR (CDCl.sub.3, 250 MHz): ?=5.08 (dd, J=12.6, 7.4 Hz, 2H), 3.85 (dd, J=7.4, 1.3 Hz, 2H), 3.10 (dd, J=12.6, 1.3 Hz, 2H), 1.45 (s, 6H), 1.25 (s, 6H).

[0802] .sup.13C NMR (CDCl.sub.3, 63 MHz): ?=106.3, 95.1, 55.7, 27.1, 21.8.

Example 1-9: Di-?-bromobis[(1,2,3-?)-3-methyl-2-butenyl]dipalladium (4-Br)

[0803] ##STR00086## [0804] Yellow solid, melting point: 119-120? C.

TABLE-US-00016 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol 3,3-dimethylallyl bromide 373 mg, 0,29 ml, 2.5 mmol Yield 82 mg, 64.2%

[0805] .sup.1H NMR (CDCl.sub.3, 300 MHz): ?=5.08 (dd, J=12.7, 7.3 Hz, 2H), 3.92 (dd, J=7.3, 1.5 Hz, 2H), 3.14 (dd, J=12.7, 1.5 Hz, 2H), 1.60 (s, 6H), 1.29 (s, 6H).

[0806] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=106.4, 97.7, 57.1, 27.7, 22.1.

Example 1-10: Di-?-chlorobis[(1,2,3-?)-1-phenyl-2-propen-1-yl]dipalladium (5-Cl) [CAS Number: 12131-44-1]

[0807] ##STR00087## [0808] Yellow solid, melting point: 201? C.

TABLE-US-00017 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol Cinnamyl chloride 803 mg, 0.73 ml, 5 mmol Yield 129 mg, >99%

[0809] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=7.44-7.56 (m, 4H), 7.31-7.40 (m, 2H), 7.22-7.31 (m, 4H), 5.80 (td, ddd, J=11.9, 11.4, 6.7 Hz, 2H), 4.62 (d, J=11.4 Hz, 2H), 3.97 (dd, J=6.7, 0.6 Hz, 2H), 3.04 (dt, J=11.9, 0.9 Hz, 2H).

[0810] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=136.9, 129.0, 128.5, 127.9, 105.9, 81.8, 59.4.

Example 1-11: Di-?-bromobis[(1,2,3-?)-1-phenyl-2-propen-1-yl]dipalladium (5-Br) [CAS Number: 32876-05-4]

[0811] ##STR00088## [0812] Orange solid, melting point: 173? C.

TABLE-US-00018 Pd(vs) Palladium content 5.35%, 993 mg, 0.5 mmol Cinnamyl 1011 mg, 0.76 ml, 5 mmol bromide Yield 151 mg, >99%

[0813] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=7.44-7.56 (m, 4H), 7.23-7.38 (m, 6H), 5.83 (ddd, J=11.9, 11.6, 6.8 Hz, 2H), 4.73 (d, J=11.6 Hz, 2H), 4.05 (d, J=6.8 Hz, 2H), 3.08 (d, J=11.9 Hz, 2H). .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=137.0, 129.0, 128.5, 128.1, 105.5, 84.3, 60.6.

Example 1-12: Di-?-chlorobis[(1,2,3-?)-2-cyclohexen-1-yl]dipalladium (6-Cl) [CAS Number: 12090-09-4]

[0814] ##STR00089## [0815] Yellow solid, melting point: 108? C.

TABLE-US-00019 Pd(vs) Palladium content Palladium content 10.9%, 5.35%, 993 mg, 1.953 g, 2 mmol 0.5 mmol 3-chlorocyclohexene 609 mg, 0.58 ml, 5 295 mg, 0.28 ml, 2.4 mmol mmol Yield 111 mg, >99% 439 mg, 98.4%

[0816] .sup.1H NMR (CDCl.sub.3, 250 MHz): ?=5.48 (t, J=6.3 Hz, 2H), 5.18 (t, J=5.3 Hz, 4H), 1.63-1.95 (m, 10H), 0.91-1.17 (m, 2H).

[0817] .sup.13C NMR (CDCl.sub.3, 63 MHz): ?=101.7, 78.8, 28.7, 19.4.

Example 1-13: Di-?-bromobis[(1,2,3-?)-2-cyclohexen-1-yl]dipalladium (6-Br) [CAS Number: 35284-31-2]

[0818] ##STR00090## [0819] Yellow solid, melting point: 129? C.

TABLE-US-00020 Pd(vs) Palladium content 10.9%, 1.953 g, 2 mmol 3-bromocyclohexene 392 mg, 0.28 ml, 2.43 mmol Yield 534 mg, 90.9%

[0820] .sup.1H NMR (CDCl.sub.3, 400 MHz): ?=5.47 (t, J=6.5 Hz, 2H), 5.30 (t, J=5.1 Hz, 4H), 1.70-1.99 (m, 10H), 1.02-1.20 (m, 2H).

[0821] .sup.13C NMR (CDCl.sub.3, 101 MHz): ?=101.7, 81.1, 28.7, 19.5.

Example 1-14: Reaction of Pd(vs) with 1-(chloromethyl)naphthalene (Preparation of 7-Cl)

[0822] ##STR00091##

[0823] A solution of Pd(vs) (palladium content 10.9%, 1945 mg, 2 mmol) was added to a solution of 1-(chloromethyl)naphthalene (446 mg, 2.4 mmol, 1.2 equiv.) in 3 ml of dried and degassed acetone in an injection vial under an argon atmosphere. After one hour, a yellow solution began to form, which continued to be stirred for 24 hours and 3 ml of hexane were added thereto. The supernatant liquid was decanted and the solid obtained was washed three times with 5 ml of acetone and dried under vacuum. 196 mg (yield: 34.6%) of a yellow solid were isolated.

[0824] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ?=8.47 (d, J=8.1 Hz, 2H), 7.91 (dd, J=19.0, 8.1 Hz, 2H), 7.53-7.73 (m, 2H), 7.36 (t, J=7.6 Hz, 1H), 7.05 (d, J=5.5 Hz, 1H), 3.88-3.88 (m, 1H), 3.90 (s, 2H) ppm.

[0825] .sup.13C NMR (101 MHz, DMSO-d.sub.6) ?=133.99, 130.03, 128.27, 128.20, 127.47, 127.45, 126.35, 125.34 ppm.

[0826] mp: >160? C. (decomposition)

[0827] IR (ATR): 950 (vw), 876 (vw), 795 (vw), 772 (w), 753 (w), 709 (vw), 644 (vw), 571 (vw), 509 (vw) cm-1.

[0828] EA Anal. Calcd for C.sub.22H.sub.18Cl.sub.2Pd.sub.2: C, 46.68, H, 3.20; N, 0.00 Found: C, 46.99H, 3.171 N, 0.00.

Example 1-15: Reaction of Pd(vs) with 2-(chloromethyl)naphthalene (Preparation of 8-Cl)

[0829] ##STR00092##

[0830] 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium Pd(vs) (1 equiv., 1945 mg, 2 mmol, 10.9% Pd) was dissolved in 3 ml of dried and degassed acetone in an injection vial containing 2-(chloromethyl)naphthalene (1.2 eq, 437 mg, 2.4 mmol, 97%). The mixture was stirred for 16h. The orange precipitate was filtered off and the solid was washed three times with 6 ml of acetone. 135 mg of product were isolated.

[0831] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ?=7.88 (s, 2H), 7.78 (t, J=6.9 Hz, 4H), 7.60-7.73 (m, 4H), 7.37-7.49 (m, 4H), 3.56 (s, 4H) ppm.

[0832] .sup.13C NMR (101 MHz, DMSO-d.sub.6) ?=125.00, 126.31, 127.20, 127.79, 127.94, 131.19, 134.01 ppm.

[0833] mp: >179? C. (decomposition).

[0834] IR (ATR): 855 (vw), 816 (w), 746 (w), 648 (vw), 614 (vw), 544 (vw), 501 (vw), 571 (vw), 509 (vw) cm-1.

[0835] EA Anal. Calcd for C.sub.22H.sub.18Cl.sub.2Pd.sub.2: C, 46.68, H, 3.20; N, 0.00 Found: C, 46.96 H, 3.380 N, 0.00.

Example 1-16: Reaction of Pd(vs) with 1-(bromomethyl)naphthalene (Preparation of 7-Br)

[0836] ##STR00093##

[0837] 1592 mg (7.2 mmol, 1.2 equiv.) of 1-(bromomethyl)naphthalene dissolved in 3 ml of dried and degassed acetone were initially charged in an injection vial and, under anhydrous and oxygen-free conditions, 5210 mg (10.9% Pd, 6 mmol, 1 equiv.) of Pd(vs) were added and stored at 4-6? C. overnight. The orange precipitate was filtered off in air and washed five times with 5 ml of acetone and dried under vacuum. 1632 mg (yield 83%) of 7-Br were obtained as an orange solid.

[0838] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 6=8.32-8.40 (m, 2H), 7.87-8.02 (m, 4H), 7.64-7.77 (m, 4H), 7.47 (dd, J=8.7, 6.4 Hz, 2H), 6.44 (d, J=6.2 Hz, 2H), 4.12 (s, 4H) ppm.

[0839] .sup.13C NMR (101 MHz, DMSO-d.sub.6) ?=124.80, 127.58, 128.57, 128.69, 129.02, 129.18, 130.31, 134.04 ppm.

[0840] Mp: >147? C. (decomposition)

[0841] IR (ATR): 1504 (vw), 1329 (vw), 1235 (vw), 951 (vw), 876 (vw), 794 (w), 772 (w), 754 (vw), 643 (vw), 571 (vw), 510 (vw) cm-1.

Example 1-17: Reaction of Pd(vs) with 2-(bromomethyl)naphthalene (Preparation of 8-Br)

[0842] ##STR00094##

[0843] 921 mg (4 mmol, 1 equiv.) of 2-(bromomethyl)naphthalene dissolved in 3 ml of dried and degassed acetone were initially charged in an injection vial and, under anhydrous and oxygen-free conditions, 4168 mg (10.9% Pd, 4.8 mmol, 1 equiv.) of Pd(vs) were added. The solution was stirred for 2 h. The orange precipitate was filtered off in air and washed three times with 5 ml of acetone. The solid was dried under vacuum, giving 540 mg (41% yield) as an orange solid.

[0844] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ?=7.85 (d, J=7.9 Hz, 2H), 7.80 (d, J=7.8 Hz, 2H), 7.74 (d, J=8.7 Hz, 2H), 7.56-7.67 (m, 4H), 7.42-7.55 (m, 4H), 3.71 (s, 4H) ppm.

[0845] .sup.13C NMR (101 MHz, DMSO-d.sub.6) ?=125.71, 126.70, 127.05, 127.83, 127.98, 129.05, 131.41, 134.50 ppm.

[0846] mp: >171? C. (decomposition)

[0847] IR (ATR): 855 (vw), 813 (vw), 766 (w), 747 (w), 650 (vw), 614 (w), 542 (w) cm.sup.?1.

[0848] EA Anal. Calcd for C.sub.22H.sub.18Br.sub.2Pd.sub.2: C, 40.34, H, 2.77; N, 0.00 Found: C, 40.35 H, 2.652 N, 0.00.

Example 1-18: Reaction of Pd(vs) with 3-(tert-butyl)-1-chloro-1H-indene (Preparation of 9-Cl)

[0849] ##STR00095##

[0850] 3-(tert-butyl)-1-chloro-1H-indene (1 equiv, 30 mg, 0.145 mmol) dissolved in 0.1 ml acetone was initially charged and Pd(vs) (1.2 equiv, 151 mg, 0.174 mmol) was added and shaken. The mixture was stored overnight at 4? C. The crystals that formed were carefully separated off and washed with a few drops of water and acetone, and dried. 29 mg (64%) of dark brown crystals were obtained.

[0851] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.09-7.19 (m, 2H), 6.83 (d, J=4.3 Hz, 8H), 5.53 (d, J=2.9 Hz, 2H), 1.32 (s, 18H) ppm.

[0852] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=141.91, 140.70, 127.45, 127.15, 120.08, 120.05, 118.64, 118.56, 107.43, 107.37, 73.01, 34.19, 28.65 ppm.

C.2 Preparation of Palladium(II) Compounds According to Formula IX, Formula IX.a or IX.b and IX.c, Formula IX.d or Formula IX.P and Formula IX.N

Example 2-1 1-methylnaphthyl[tris(tert-butyl)phosphine]bromopalladium(II) (10-Br)

[0853] ##STR00096##

[0854] 7-Br (1 eq, 164 mg, 0.25 mmol) was added to a vial and the air was replaced with argon. The solid was dissolved in 20 ml of dry and degassed THE and the vial was transferred to the glove box. Tri-tert-butylphosphine, (2 eq, 103 mg, 0.5 mmol, 98%) was then added and the reaction mixture was stirred for 30 min at room temperature. The suspension was filtered with a syringe filter and the filtrate reduced to 90% of the volume. Hexane was then added and the sample was stored in the freezer (?20? C.) to precipitate the product. The crude reaction mixture was washed with pentane and the remaining solid was dissolved in toluene and filtered over Celite?. The solvent was removed under reduced pressure to give 216 mg (82%) of an orange solid.

[0855] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=7.73 (s, 2H), 7.57 (t, J=7.6 Hz, 1H), 7.41 (d, J=7.8 Hz, 1H), 7.31 (t, J=7.1 Hz, 1H), 7.23 (t, J=8.1 Hz, 1H), 6.32 (t, J=5.4 Hz, 1H), 3.35 (br. s, 2H), 1.31 (d, J=12.5 Hz, 27H) ppm.

[0856] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) ?=131.85 (d, J=3.70 Hz), 130.77 (d, J=4.40 Hz), 129.55, 128.72, 127.96, 123.63, 109.58 (d, J=13.91 Hz), 40.24 (d, J=5.80 Hz), 37.87, 33.11 ppm.

[0857] .sup.31P NMR (162 MHz, C.sub.6D.sub.6) ?=99.92 ppm;

[0858] Elemental analysis calculated C.sub.23H.sub.36BrPPd: C, 52.14, H, 6.85, N, 0.00; found: C, 51.86 H, 6.28 N, 0.00.

Example 2-2 1-methylnaphthyl[tris(cyclohexyl)phosphine]bromopalladium(II) (11-Br)

[0859] ##STR00097##

[0860] 7-Br (1 eq, 164 mg, 0.25 mmol) was added to a vial, the air was replaced with argon and the vial was transferred to the glove box. Tricyclohexylphosphine (2 eq, 140 mg, 0.5 mmol) was then added, followed by 20 ml of THF. The reaction mixture was stirred for 90 min at room temperature. 90% of the solvent was evaporated and 10 ml of pentane was added. The sample was stored overnight at ?20? C. to crystallize the product. The mother liquor was decanted and the solid was dried under high vacuum to give 192 mg (63%) of a yellow solid.

[0861] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) ?=7.87 (d, J=7.8 Hz, 1H), 7.78 (d, J=7.6 Hz, 1H), 7.71 (d, J=7.3 Hz, 1H), 7.40-7.61 (m, 3H), 6.12 (t, J=5.6 Hz, 1H), 3.71-4.05 (br. s, 1H), 2.54 (br. s, J=1.2 Hz, 1H), 2.00-2.18 (m, 3H), 1.53-1.96 (m, 15H), 1.02-1.44 (m, 15H) ppm.

[0862] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) ?=135.3 (d, J=2.9 Hz), 131.0 (d, J=5.1 Hz), 129.6 (s), 129.1 (s), 129.0 (s), 127.5 (s), 124.0 (s), 120.5 (d. J=3.7 Hz), 100.3 (s), 100.2 (s), 37.5 (d, J=4.4 Hz), 35.7 (d, J=19.8 Hz), 30.8 (d, J=25.7 Hz), 28.1 (d, J=11 Hz), 26.9 (s) ppm.

[0863] .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) ?=53.91 ppm.

[0864] Elemental analysis calculated C.sub.29H.sub.42BrPPd*THF(C.sub.4H.sub.8thO): C, 58.28, H, 7.41, N, 0.00; found: C, 58.65 H, 6.32 N, 0.00.

Example 2-3 1-methylnaphthyl[tris(cyclohexyl)phosphine]chloropalladium(II) (11-Cl)

[0865] ##STR00098##

[0866] 7-Cl (1 eq, 142 mg, 0.25 mmol) was added to a vial, the air was replaced with argon and the vial was transferred to the glove box. Tricyclohexylphosphine (2 eq, 140 mg, 0.5 mmol) was then added, followed by 20 ml of THF. The reaction mixture was stirred for 90 min at room temperature. 90% of the solvent was evaporated and 10 ml of pentane was added. The sample was stored overnight at ?20? C. to precipitate the product. The solution was decanted from the solid and the remaining solid was washed with pentane (3?5 ml) and dried under high vacuum to afford 91 mg (32%) of a yellow solid.

[0867] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): ?=7.96 (d, J=7.6 Hz, 1H), 7.88 (d, J=7.3 Hz, 1H), 7.84 (dd, J=8.8, 3.2 Hz, 1H), 7.57-7.68 (m, 2H), 7.53 (t, J=7.6 Hz, 1H), 6.26 (t, J=5.7 Hz, 1H), 3.82 (br. s., 1H), 2.57 (br. s., 1H), 2.05-2.21 (m, 3H), 1.65-1.97 (m, 15H), 1.16-1.51 (m, 15H).

[0868] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2): ?=135.43 (d, J=2.93 Hz), 130.4, 130.4, 129.5, 129.1, 129.0, 127.5, 124.1, 120.81 (d, J=3.67 Hz), 100.67 (d, J=19.07 Hz), 35.35, 35.16, 28.13, 28.02, 26.93 (d, J=1.50 Hz) ppm.

[0869] .sup.31P NMR (162 MHz, C.sub.6D.sub.6): ?=53.53 ppm.

[0870] HRMS (TOF-EI): m/z calculated for C.sub.14H.sub.18O.sub.3: 562.1747 [M].sup.+; found 562.1772.

Example 2-4 1-methylnaphthyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]bromopalladium(II) (12-Br)

[0871] ##STR00099##

[0872] In a glove box filled with nitrogen, 164 mg of 7-Br (1 eq., 0.25 mmol) and 224 mg of IPr (2 eq., 0.5 mmol) were added into a crimp-cap vial. 20 ml of diethyl ether were then added and the reaction mixture was stirred for 90 min under a nitrogen atmosphere. 90% of the solvent was evaporated and 20 ml of pentane was added. The sample was stored overnight at ?20? C. to crystallize the product. The mother liquor was decanted and the remaining solid was washed with pentane (3?2 ml) and dried under high vacuum to afford 325 mg (91%) of a yellow solid.

[0873] .sup.1H NMR (400 MHz, C.sub.6D.sub.6; 283K) ?=7.32-7.43 (m, 2H), 7.21-7.32 (m, 4H), 7.07-7.21 (m, 3H, overlap with solvent signal), 6.99 (br. s, 2H), 6.86 (d, J=8.1 Hz, 1H), 6.55 (s, 2H), 5.40 (d, J=6.5 Hz, 1H), 3.52-3.64 (m, 2H), 3.38 (br. s., 1H), 1.88 (br. s., 1H), 1.44-1.64 (m, 6H), 1.39 (dt, J=6.6, 3.3 Hz, 2H), 0.78-1.25 (m, 18H) ppm.

[0874] .sup.13C NMR (101 MHz, C.sub.6D.sub.6; 283K) ?=184.63, 146.76, 136.94, 135.42, 132.92, 130.49, 130.04, 128.97, 127.21, 124.79, 124.41, 119.00, 91.88, 68.14, 33.85, 26.38, 23.09, 14.59 ppm.

[0875] HRMS (TOF-EI) m/z calculated C.sub.38H.sub.45BrN.sub.2Pd [M].sup.+ 714.1800, found 714.1786.

Example 2-5 2-methylnaphthyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]bromopalladium(II) (13-Br)

[0876] ##STR00100##

[0877] In a glove box filled with nitrogen, 164 mg of 8-Br (1 eq., 0.25 mmol) and 224 mg of IPr (2 eq., 0.5 mmol) were added into a crimp-cap vial. 20 ml of diethyl ether were then added and the reaction mixture was stirred for 90 min under a nitrogen atmosphere. 90% of the solvent was evaporated and 20 ml of pentane was added. The sample was stored overnight at ?20? C. to crystallize the product. The mother liquor was decanted and the remaining solid was washed with pentane (3?2 ml) and dried under high vacuum to afford 344 mg (96%) of a yellow solid.

[0878] .sup.1H NMR (300 MHz, C.sub.6D.sub.6) ?=7.69 (d, J=7.9 Hz, 1H), 7.18-7.30 (m, 4H), 7.08-7.17 (m, 6H, overlap with solvent signal), 6.63 (s, 2H), 6.11 (dd, J=8.8, 1.7 Hz, 1H), 5.59 (s, 1H), 3.22 (spt, J=7.0 Hz, 4H), 2.52 (br. s., 2H), 1.30-1.50 (m, 12H, overlap with THE signal), 1.01 (d, J=7.0 Hz, 12H) ppm.

[0879] .sup.13C NMR (75 MHz, THF-d8) ?=184.19, 147.37, 138.61, 137.78, 132.66, 132.54, 130.53, 130.48, 128.48, 127.51, 126.45, 126.09, 124.75, 124.26, 119.41, 91.88, 40.14, 29.50, 27.93, 26.50, 23.54 ppm.

[0880] Elemental analysis calculated for C.sub.38H.sub.45BrN.sub.2Pd: C, 63.74, H, 6.33, N, 3.76 found: C, 64.14 H, 6.46, N, 3.91.

[0881] HRMS (TOF-EI) m/z calculated for C.sub.38H.sub.45BrN.sub.2Pd [M].sup.+ 714.1800, found 714.1802.

Example 2-6 1-methylnaphthyl[2-(dicyclohexylphosphino)-2,4,6-triisopropylbiphenyl]bromopalladium(II) (14-Br)

[0882] ##STR00101##

[0883] 7-Br (1 eq, 164 mg, 0.25 mmol) and 2-(dicyclohexylphosphino)-2,4,6-triisopropylbiphenyl (2 eq, 246 mg, 0.5 mmol, 97%) were added to a vial and the air was replaced with argon. 10 ml of THE were then added. The reaction mixture was stirred for 90 min at room temperature. The solution was concentrated to 90% volume and was overlayed with 10 ml of hexane. The vial was then stored in the freezer (?20? C.) to precipitate the product. The mother liquor was decanted and the remaining solid was washed with pentane (3?5 ml) and dried under high vacuum to afford 322 mg (80%) of a yellow solid.

[0884] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) ?=7.77-7.97 (m, 4H), 7.51-7.70 (m, 3H), 7.33-7.47 (m, 2H), 7.08-7.28 (m, 3H), 6.19 (t, J=5.7 Hz, 1H), 2.96 (spt, J=6.8 Hz, 1H), 2.66 (br. s., 2H), 2.04-2.17 (m, 2 h), 0.63-1.79 (m, 40H) ppm.

[0885] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) ?=149.6, 147.0, 142.3, 138.4, 138.2, 136.8, 135.2, 134.4 (two peaks), 130.8 (two peaks), 129.4, 128.7-129.2 (m, complex coupling pattern), 127.4, 126.0, 125.9, 124.1, 121.6, 120.9 (two peaks), 34.8, 31.2, 27.6 (two peaks), 27.2 (two peaks), 26.2, 26.1, 24.2, 22.8 (br. s.) ppm.

[0886] .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) ?=63.74 (br. S) ppm.

[0887] Elemental analysis calculated for C.sub.44H.sub.58BrPPd: C, 65.71, H, 7.27, N, 0.00, found: C, 65.73 H, 7.384, N, 0.62.

Example 2-7 1-methylnaphthyl[2-dicyclohexylphosphino-2,6-di-i-propoxy-1,1-biphenyl]bromopalladium(II) (15-Br)

[0888] ##STR00102##

[0889] 7-Br (1 eq, 164 mg, 0.25 mmol) was added to a vial, the air was replaced with argon and the vial was transferred to the glove box. 2-dicyclohexylphosphino-2,6-di-i-propoxy-1,1-biphenyl (2 eq, 238 mg, 0.5 mmol, 98%) was then added, followed by 20 ml of THF. The reaction mixture was stirred for 90 min at room temperature. 90% of the solvent was evaporated and 10 ml of pentane was added. The sample was stored overnight at ?20? C. to crystallize the product. The mother liquor was decanted and the remaining solid was washed with pentane (3?5 ml) and dried under high vacuum to afford 315 mg (79%) of a yellow solid.

[0890] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) ?=7.86 (d, J=7.8 Hz, 1H), 7.78 (d, J=8.1 Hz, 2H), 7.60-7.72 (m, 2H), 7.48-7.60 (m, 2H), 7.37-7.47 (m, 1H), 7.24-7.35 (m, 2H), 6.95 (d, J=6.1 Hz, 1H), 6.64 (d, J=8.3 Hz, 2H), 6.07 (br. s., 1H), 4.36-4.66 (m, 2H), 3.27 (br. s, 2H), 2.00-2.17 (m, 2H), 1.39-1.97 (m, 10H), 0.67-1.37 (m, 22H) ppm.

[0891] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) ?=157.5, 139.6, 137.8, 137.6, 135.2, 133.3 (two peaks), 132.0, 131.7, 130.9 (two peaks), 129.5, 129.2, 128.8, 128.5 (two peaks), 127.1, 125.5 (two peaks), 124.6, 121.3, 107.0, 99.4 (two peaks), 71.5, 44.3 (two peaks), 35.2, 34.9, 29.4, 27.6, 27.4, 27.0, 26.9, 26.4, 22.5, 22.3 ppm.

[0892] .sup.31P NMR (162 MHz, CD.sub.2C.sub.12) ?=60.62 (br. s.) ppm.

[0893] Elemental analysis calculated for C.sub.41H.sub.52BrO.sub.2PPd: C, 62.01, H, 6.60, N, 0.00; found: C, 61.59, H, 6.49, N, 0.00.

Example 2-8 1-methylnaphthyl[2-dicyclohexylphosphino-2,6-di-i-propoxy-1,1-biphenyl]chloropalladium(II) (15-Cl)

[0894] ##STR00103##

[0895] 7-Cl (1 eq, 142 mg, 0.25 mmol) was added to a vial, the air was replaced with argon and the vial was transferred to the glove box. 2-dicyclohexylphosphino-2,6-di-i-propoxy-1,1-biphenyl (2 eq, 238 mg, 0.5 mmol, 98%) was then added, followed by 20 ml of THF. The reaction mixture was stirred for 90 min at room temperature. 90% of the solvent was evaporated and 10 ml of pentane was added. The sample was stored overnight at ?20? C. to crystallize the product. The mother liquor was decanted and the remaining solid was washed with pentane (3?5 ml) and dried under high vacuum to afford 311 mg (83%) of a yellow solid.

[0896] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) ?=7.66-7.84 (m, 3H), 7.45-7.66 (m, 3H), 7.41 (t, J=7.5 Hz, 1H), 7.29-7.37 (m, 1H), 7.16-7.28 (m, 2H), 6.87 (d, J=7.1 Hz, 1H), 6.55 (d, J=8.3 Hz, 2H), 6.00 (t, J=5.8 Hz, 1H), 4.41 (spt, J=12.0 Hz, 2H), 2.99 (br. s., 2H), 1.98 (q, J=10.9 Hz, 2H), 1.69 (br. s., 4H), 1.31-1.59 (m, 7H), 0.66-1.29 (m, 21H) ppm.

[0897] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) ?=157.5, 139.7, 137.6 (two peaks), 135.4, 133.3 (two peaks), 131.9, 131.5, 130.3 (two peaks), 129.4, 129.2, 129.1, 128.8, 128.4 (two peaks), 127.0, 125.5 (two peaks), 124.6, 121.7, 107.0, 100.0 (two peaks), 71.4, 41.3, 34.7 (two peaks), 31.5, 29.4, 27.5 (two peaks), 27.0 (two peaks), 26.4, 22.6, 22.2 ppm.

[0898] .sup.31P NMR (162 MHz, CD.sub.2Cl.sub.2) ?=59.08 (br. s.) ppm.

[0899] Elemental analysis calculated for C.sub.41H.sub.52ClO.sub.2PPd: C, 65.69, H, 6.99, N, 0.00; found: C, 65.73 H, 6.57, N, 0.00.

Example 2-9 1-methylnaphthyl[bis(1-adamantyl)butyl]bromopalladium(II) (16-Br)

[0900] ##STR00104##

[0901] In a glove box filled with nitrogen, 7-Br (1 eq, 82 mg, 0.125 mmol) and butyldi-1-adamantylphosphine (2 eq, 90 mg, 0.25 mmol) were added to a 40 ml crimp-cap vessel. The vial was capped and removed from the glove box. 20 ml of dry and degassed THE were added and the reaction mixture was stirred for 1.5 h at room temperature. 90% of the solvent was removed under high vacuum and 15 ml of hexane were added. The vial was then stored for 16 h at ?20? C. The solution was separated from the solid and the remaining solid was washed with pentane (3?5 ml). After drying under high vacuum, 131 mg (76%) of a light yellow solid were obtained.

[0902] .sup.1H NMR (400 MHz, C.sub.4OD.sub.8) ?=8.02 (d, J=8.1 Hz, 1H), 7.82 (d, J=7.7 Hz, 1H), 7.66-7.74 (m, 1H), 7.44-7.62 (m, 3H), 6.09-6.21 (m, 1H), 2.47 (br. s, 1H), 2.14-2.34 (m, 3H), 1.83-2.09 (m, 6H), 1.59-1.82 (m, 14H), 1.39-1.58 (m, 7H), 1.08-1.38 (m, 10H) ppm.

[0903] .sup.13C NMR (101 MHz, C.sub.4OD.sub.8) ?=136.11 (s), 132.12 (d, J=4.98 Hz), 130.15 (s), 129.93 (s), 129.12 (d, J=4.98 Hz), 129.04 (s), 127.49 (s), 124.61 (s), 121.41 (s), 99.30 (d, J=19.90 Hz), 37.73 (s), 36.17 (d, J=19.90 Hz), 31.27 (s), 28.51 (d, J=11.61 Hz), 27.43 (s), 26.01 (s, overlap with solvent signal) ppm.

[0904] .sup.31P NMR (162 MHz, C.sub.4OD.sub.8) ?=52.02 ppm.

[0905] HRMS (TOF-EI) m/z calculated for C.sub.35H.sub.47BrPPd [M].sup.+ 684.1712, found 684.1729.

Example 2-10 2-methylnaphthyl[bis(1-adamantyl)butyl]bromopalladium(II) (17-Br)

[0906] ##STR00105##

[0907] In a glove box filled with nitrogen, 8-Br (1 eq, 164 mg, 0.25 mmol) and butyldi-1-adamantylphosphine (2 eq, 179 mg, 0.5 mmol) were added to a 40 ml crimp-cap vial. The vial was capped and removed from the glove box. 20 ml of dry and degassed THE were added and the reaction mixture was stirred for 1.5 h at room temperature. The solvent was removed under reduced pressure and the remaining solid was washed with small portions of pentane. After drying under high vacuum, 276 mg (78%) of a light yellow solid were obtained.

[0908] .sup.1H NMR (400 MHz, C.sub.6D.sub.6) ?=8.06 (d, J=8.1 Hz, 1H), 7.33-7.50 (m, 3H), 7.24 (t, J=7.6 Hz, 1H), 6.80 (d, J=8.8 Hz, 1H), 6.37 (d, J=4.9 Hz, 1H), 3.17-3.72 (m, 1H), 2.37-2.82 (m, 1H), 1.97-2.29 (m, 15H), 1.84 (br. s., 6H), 1.44-1.70 (m, 15H), 0.97 (t, J=7.2 Hz, 3H).

[0909] .sup.13C NMR (101 MHz, CD.sub.2Cl.sub.2) ?=136.66, 133.06 (d, J=1.50 Hz), 130.37 (d, J=2.20 Hz), 128.67 (d, J=2.20 Hz), 127.93 (d, J=1.50 Hz), 127.58 (d, J=2.20 Hz), 124.67, 118.46, 103.37, 103.04, 41.37 (d, J=3.66 Hz), 40.62, 37.76 (d, J=2.93 Hz), 36.97, 35.95, 30.08, 29.31 (d, J=8.80 Hz), 28.36 (d, J=8.80 Hz), 25.82 (d, J=13.91 Hz), 20.82 (d, J=18.30 Hz), 14.22 ppm.

[0910] .sup.31P NMR (162 MHz, C.sub.6D.sub.6) ?=64.44 ppm.

[0911] HRMS (TOF-EI) m/z calculated for C.sub.35H.sub.47PPd [M].sup.+ 684.1712, found 684.1740.

Example 2-11 Preparation of [Pd(cataCXium? A)(allyl)Cl], [(Di(1-adamantyl)-n-butylphosphine)(?.SUP.3.-allyl)chloro]palladium (IX.P)

[0912] ##STR00106##

[0913] 22.5 ml of degassed acetone were initially charged in a three-necked flask inertized with argon and then 1.00 g of [Pd(allyl)Cl].sub.2, bis(?.sup.3-allyl)di(?-chloro)dipalladium(II), (2.73 mmol, 1.0 eq) and 1.96 g of cataCXium? A, di(1-adamantyl)-n-butylphosphine, (5.47 mmol; 2.0 eq) were added in succession. A whitish solid already precipitated out about a minute after everything was mixed together. The reaction mixture was stirred for 20 hours at room temperature under an inert atmosphere and filtered over a D4 frit the next morning. The isolated solid was washed twice with 7 ml methanol each time in suspension and then dried overnight at room temperature in a vacuum drying cabinet. In this case, it was possible to isolate 2.77 g of whitish product [(di(1-adamantyl)-n-butylphosphine)(?.sup.3-allyl)chloro]palladium at a yield of 93.0%. .sup.31P{.sup.1H} NMR (101 MHz, toluene): ?=53 ppm.

Example 2-12 Preparation of [Pd(cataCXium? A)(allyl)Cl], [(Di(1-adamantyl)-n-butylphosphine)(?.SUP.3.-allyl)chloro]palladium (IX.P) using one-pot synthesis

[0914] 5.15 g of Pd(vs), 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0) (1.21 mmol; 1 eq; CAS number: 252062-59-2), and 0.97 g of cataCXium? A, di(1-adamantyl)-n-butylphosphine (2.66 mmol, 2.20 eq) were initially charged in a 50 ml three-necked flask inertized with argon, and the containers used were flushed with 12 ml of acetone thereafter. The resulting suspension was stirred for one hour at room temperature under argon, during which time the color of the mother liquor changed from yellow to light beige to virtually colorless. 0.19 g of allyl chloride (2.42 mmol, 2 eq) were then added and the reaction mixture was stirred overnight at room temperature. A cream-colored suspension formed, which was filtered over an argon-blanketed D4 frit. The filter cake was washed three times in suspension with 5 ml methanol each time and dried overnight at room temperature in a vacuum drying cabinet. It was possible to isolate 1.18 g of cream-colored solid at a yield of 90%.

[0915] .sup.31P{.sup.1H} NMR (101 MHz, toluene): ?=53 ppm.

[0916] Silicon content by means of ICP-AES=310 ppm.

Example 2-13 Preparation of [Pd(cataCXium? A)(allyl)Cl], [(Di(1-adamantyl)-n-butylphosphine)(?.SUP.3.-allyl)chloro]palladium (IX.P) using one-pot synthesis

[0917] 5.15 g of Pd(vs)c, 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0) (1.21 mmol; 1 eq; CAS number: 252062-59-2), and 0.19 g of allyl chloride (2.42 mmol, 2 eq) were initially charged in a 50 ml three-necked flask inertized with argon, and the containers used were flushed with 12 ml of acetone thereafter. The resulting suspension was stirred for one hour at room temperature under argon, during which time a light yellow solid precipitated. Subsequently, 0.97 g of cataCXium? A, di(1-adamantyl)-n-butylphosphine (2.66 mmol, 2.20 eq) was added. After stirring for approximately 10 minutes, a cream-colored solid precipitated. The reaction mixture was stirred overnight at room temperature. A cream-colored suspension formed, which was filtered over an argon-blanketed D4 frit. The filter cake was washed three times in suspension with 5 ml methanol each time and dried overnight at room temperature in a vacuum drying cabinet. It was possible to prepare 0.94 g of creamy-white [(di(1-adamantyl)-n-butylphosphine)(N.sup.3-allyl)chloro]palladium at a yield of 85%.

[0918] .sup.31P{.sup.1H} NMR (101 MHz, toluene): ?=53 ppm.

[0919] Silicon content by means of ICP-AES=30 ppm.

Example 2-14 Preparation of [Pd(cataCXium? A)(1-.SUP.t.Bu-Ind)Cl], chloro[(1-tert-butyl-1H-inden-1-yl)(1-adamantyl)n-butylphosphine]palladium

[0920] 1.15 g of cataCXium? A, di(1-adamantyl)-n-butylphosphine (3.20 mmol; 2.0 eq) were initially charged in a three-necked flask inertized with argon, and 25 ml of acetone were added thereto. 1.00 g of di-?-chlorobis(1-tert-butyl-1H-inden-1-yl)dipalladium(II) (1.60 mmol; 1.0 eq) were then added, with stirring, and flushing was carried out with 25 ml of acetone. A dark brown suspension was briefly present, which changed color to reddish brown after stirring for about 1 minute. The reaction mixture was boiled at reflux temperature for four hours. In the process, the color changed from red-brown to orange-red. The product suspension was then cooled and the precipitated solid was filtered over a D4 frit, washed twice with 7.5 ml of methanol each time in suspension and dried under vacuum overnight at room temperature. It was possible to isolate 2.03 g of orange-red product chloro[(1-tert-butyl-1H-inden-1-yl)(1-adamantyl)n-butylphosphine]palladium. The yield was 94%.

[0921] .sup.31P{.sup.1H} NMR (101 MHz, CD.sub.2Cl.sub.2): ?=60 ppm.

Example 2-15 Preparation of [(IPr)Pd(allyl)Cl)], allylchloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) (IX.N) using one-pot synthesis

[0922] 200 ml of isopropanol were initially charged in a 500 ml reactor inertized with argon. 100 g of Pd(vs), 1,3-divinyl-1,1,3,3-tetramethyldisiloxanepalladium(0) (24.18 mmol; 1 eq; CAS number: 252062-59-2) were added and the container used was flushed with 50 ml of isopropanol. 4.9 g of allyl chloride (98%; 62.75 mmol; 2.60 eq) were then added dropwise within 2 minutes using a dropping funnel. A light yellow, fine solid precipitated. The internal temperature increased slightly from 18.5? C. to 19.7? C. The dropping funnel was flushed with 20 ml of isopropanol and the reaction mixture was stirred for a further hour at room temperature. 23.14 g of IPr*HCl, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (53.20 mmol; 2.20 eq) and 2.2 eq of base (for example an alkali metal hydroxide or alkoxide) were then added to the reaction mixture and the containers used were flushed with 30 ml of isopropanol. The mixture was stirred overnight at room temperature under an argon blanket, and a clear orange solution formed after one hour. The next morning, the reaction mixture was concentrated on a rotary evaporator. 55 ml of petroleum ether were added to the resulting suspension and the solid was filtered over a D4 frit in air. The filter cake was washed twice in suspension with 60 ml of petroleum ether 50-70 and dried overnight in a vacuum drying cabinet at room temperature. It was possible to isolate 25.46 g of cream-colored allylchloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]palladium(II) at a yield of 92.1%.

[0923] Silicon content by means of ICP-AES=190 ppm.

C.3 Examples Relating to Catalytic Activity

3.1 Test of the Dimeric Allylpalladium Halide Complexes According to General Formula VIII in Suzuki-Miyaura Cross-Coupling Reactions

[0924] A. Suzuki-Miyaura Coupling of 3-Chloropyridine with p-Tolylboronic Acid

[0925] The Suzuki-Miyaura coupling of 3-chloropyridine with p-tolylboronic acid was chosen as a model reaction to verify the catalytic activity of the allylpalladium precatalysts. This reaction was investigated by Colacot et al. and yields of the coupling product of 91% were found after 30 minutes reaction time with the precatalyst 3-Cl-Xphos (Colacot T. J. et al., Journal of Organic Chemistry, 2015, 80, 6794).

[0926] The use of only 0.5 mol % of 3-Cl-Xphos led to yields of 39-62% of the expected biaryl compound (table 1, no. 3). This condition was used to compare different precatalysts. The allylpalladium halide-phosphine complexes were produced in situstirring the allylpalladium halide with the phosphine Xphos prior to addition of the reaction partners. The unsubstituted allylpalladium halide was less active than 3-Cl-Xphos (see tables 1 and 2 below). Allylpalladium chlorides (1 Cl) generally resulted in yields of 50-65%, even at catalyst loadings of 1 mol %; (Pd 2 mol %). Allylpalladium bromide (1 Br) was less active than comparable chlorides. Other precatalysts, with the exception of 6-Cl and 6-Br, gave comparable reactivities to L1 with slight differences in chloride and bromide complexes. The Hazari precatalyst was also tested and also showed activity.

##STR00107##

TABLE-US-00021 TABLE B-1 Suzuki-Miyaura cross-couplings. [00108] [00109] Catalyst loading Ligand No. Catalyst [mol %] [mol %] Yield [%].sup.a) 1 3-Cl-Xphos 2 89 2 3-Cl-Xphos 1 76.sup.b) 3 3-Cl-Xphos 0.5 60 4 1-Cl 1 2 60 5 1-Br 1 2 49 6 1-I 1 2 0 7 2-Cl 1 2 97.sup.b) 8 2-Cl 0.25 0.5 59 9 2-Br 1 2 95.sup.b) 10 2-Br 0.25 0.5 60 11 3-Cl 1 2 93.sup.b) 12 3-Cl 0.25 0.5 65 13 3-Br 0.25 0.5 59 14 4-Cl 1 2 91.sup.b) 15 4-Cl 0.25 0.5 63 16 4-Br 0.25 0.5 56 17 5-Cl 0.25 0.5 65 18 5-Br 0.25 0.5 58 19 6-Cl 0.25 0.5 55 20 6-Br 0.25 0.5 49 21 9-Cl 0.5 0.5 55

[0927] A dried injection vial was charged with the allyl palladium halide dimer (x eq, x mmol) and Xphos (x eq, x mmol) and the air therein was removed by evacuating and flushing with argon three times. 1 ml of dried, degassed THE (tetrahydrofuran) was then added and the mixture was stirred for 30 minutes. 3-chloropyridine (1 eq, 115 mg, 1 mmol) and p-tolylboronic acid (1.5 eq, 204 mg, 1.5 mmol) dissolved in 1 ml of THE were then added, followed by 4 ml of K3P04, 0.5 M solution. Stirring was carried out for 1 hour at 25? C., the yield was determined by gas chromatography (n-tetradecane as internal standard). [0928] a) Yield determined by gas chromatography, average of two measurements, unless otherwise stated. [0929] b) Only one measurement performed.

TABLE-US-00022 TABLE B-2 Direct comparison of the new systems with different catalyst loadings in Suzuki-Miyaura cross-coupling. [00110] [00111] Catalyst/ Catalyst 1 mol % 0.5 mol % 0.25 mol % loading Yield [%].sup.a) Yield [%].sup.a) Yield [%].sup.a) 7-Cl 71 49 34 8-Cl 92 79 65 7-Br 73 45 34 8-Br 92 76 69 .sup.a)Yield determined by gas chromatography, average of two measurements, unless otherwise stated.

[0930] A dried injection vial was charged with the allyl palladium halide dimer (x eq, x mmol) and Xphos (x eq, x mmol) and the air therein was removed by evacuating and flushing with argon three times. 1 ml of dried, degassed THE (tetrahydrofuran) was then added and the mixture was stirred for 30 minutes. 3-chloropyridine (1 eq, 115 mg, 1 mmol) and p-tolylboronic acid (1.5 eq, 204 mg, 1.5 mmol) dissolved in 1 ml of THE were then added, followed by 4 ml of K3P04, 0.5 M solution. Stirring was carried out for 1 hour at 25? C., and the yield was determined by gas chromatography (n-tetradecane as internal standard, average of two measurements).

B. Suzuki-Miyaura Cross-Coupling of 4-Chloroanisole and Isopropylboronic Acid

[0931] The above palladium-naphthyl catalysts (7-8 Cl/Br) were also tested for activity in Suzuki-Miyaura cross-coupling reactions of 4-chloroanisole and isopropylboronic acid as model compounds. Under the following reaction conditions, catalysts 7-Cl and 7-Br (substitution in the 1-position) were equally reactive and showed higher activity than catalysts 8-Cl and 8-Br (substitution in the 2-position).

TABLE-US-00023 TABLE B-3 Use in Suzuki-Miyaura coupling of secondary boronic acids. [00112] Entry Catalyst Yield [%] 1 7-Cl 87 2 7-Br 89 3 8-Cl 61 4 8-Br 65

[0932] The reactions were carried out analogously to the conditions under B-1 and B.sub.2 above, but on a 0.25 mmol scale, also under an inert gas atmosphere, using 1 equivalent of 4-chloroanisole and 1.5 equivalents of isopropylboronic acid in 0.5 ml of toluene and 0.25 ml of water as solvents. Yields were determined by gas chromatography using n-tetradecane as internal standard, also analogously to B-1 and B-2.

[0933] Further examples for Suzuki-Miyaura coupling reactions of secondary boronic acids without catalyst activation

[0934] General Procedure:

[0935] A vial was filled with the respective catalyst (0.005 mmol, 0.01 eq.), 5.86 mg of PtBu.sub.3*HBF.sub.4 (0.02 mmol, 0.04 eq.), 208 mg of K.sub.2CO.sub.3 (1.5 mmol, 3.0 eq.) and the boronic acid (0.75 mmol, 1.5 eq.), under air. After three alternating vacuum/argon cycles, a solution of the aryl chloride (0.5 mmol, 1.0 eq.) and 30 ?l of n-tetradecane in 1 ml of toluene was added with a syringe, followed by 0.5 ml of water. The resulting homogeneous solution was stirred for 11 hours at 80? C. After completion of the reaction, the mixture was diluted with diethyl ether (10 ml) and washed with water (2?10 ml). The combined organic phases were dried over MgSO.sub.4, filtered, and the volatile components were removed at 300 mbar. The residue was purified by flash column chromatography (SiO2, pentane/diethyl ether gradient), giving the desired product.

a) 4-isopropyltoluene [CAS: 99-87-6]

[0936] ##STR00113## [0937] Catalyst/Pd source: 1 mol % 7-Br [0938] Aryl chloride: 64.6 mg of 4-chlorotoluene [0939] Boronic acid: 65.9 mg of isopropylboronic acid [0940] Yield: 66.0 mg (98%) colorless liquid.

[0941] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.12-7.24 (m, 4H), 2.94 (spt, J=6.8 Hz, 1H), 2.39 (s, 3H), 1.31 ppm (d, J=6.8 Hz, 6H).

[0942] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=145.9, 135.1, 129.0, 126.3, 33.7, 24.1, 20.9 ppm.

[0943] MS (EI) m/z (%) 134.1 (33) [M+], 119.1 (100), 103.0 (5), 91.0 (22), 77.0 (6), 65.0 (5), 57.8 (2).

[0944] The NMR data is in agreement with the data in the literature (D.-H. Liu, H.-L. He, Y.-B. Zhang, Z. Li, Chem. Eur. J. 2020, 38, 14322-14329).

b) 4-isopropylacetophenone [CAS: 645-13-6]

[0945] ##STR00114## [0946] Catalyst/Pd source: 1 mol % 7-Br [0947] Aryl chloride: 79.7 mg of 4-chloroacetophenone [0948] Boronic acid: 65.9 mg of isopropylboronic acid [0949] Yield: 68.2 mg (84%) colorless liquid.

[0950] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.89 (d, J=8.8 Hz, 1H), 7.30 (d, J=6.6 Hz, 2H), 2.95 (spt, J=6.9 Hz, 1H), 2.51-2.59 (m, 3H), 1.26 ppm (d, J=7.0 Hz, 6H).

[0951] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=197.5, 154.3, 134.8, 128.4, 126.4, 34.0, 26.3, 23.4 ppm.

[0952] HRMS (TOF-EI) m/z calculated for C.sub.11H.sub.14O 162.1045 [M].sup.+; found 162.1041.

[0953] The NMR data is in agreement with the data in the literature (Z.-L. Shen, K. K. K. Goh, Y.-S. Yang, Y.-C. Lai, C. H. A. Wong, H.-L. Cheong, T.-P. Loh, Angew. Chem. Int. Ed. 2011, 50, 511-514).

c) Ethyl-4-isopropylbenzoate [CAS: 19024-50-1]

[0954] ##STR00115## [0955] Catalyst/Pd source: 1 mol % 7-Br [0956] Aryl chloride: 94.2 mg of ethyl-4-chlorobenzoate [0957] Boronic acid: 65.9 mg of isopropylboronic acid [0958] Yield: 74.6 mg (78%) colorless liquid.

[0959] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.98 (d, J=8.4 Hz, 2H), 7.29 (d, J=8.4 Hz, 2H), 4.38 (q, J=7.3 Hz, 2H), 2.97 (spt, J=7.0 Hz, 1H), 1.40 (d, J=7.3 Hz, 3H), 1.27 ppm (d, J=6.9 Hz, 6H).

[0960] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=166.7, 154.2, 129.7, 128.1, 126.4, 60.7, 34.2, 23.7, 14.3 ppm.

[0961] MS (EI) m/z (%) 192.1 (46) [M+], 177.1 (99), 164.1 (22), 147.1 (100),131.0. (14), 119.1 (50), 105.0 (27).

[0962] The NMR data is in agreement with the data in the literature (G. Cahiez, L. Foulgoc, A. Moyeux, Angewandte Chemie International Edition 2009, 48, 2969-2972).

d) 4-isopropylnitrobenzene [CAS: 1817-47-6]

[0963] ##STR00116## [0964] Catalyst/Pd source: 1 mol % 7-Br [0965] Aryl chloride: 72.7 mg of 4-chloroanisole [0966] Boronic acid: 65.9 mg of isopropylboronic acid [0967] Yield: 66.8 mg (88%) colorless liquid.

[0968] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=8.14 (d, J=8.1 Hz, 2H), 7.37 (d, J=8.1 Hz, 2H), 3.01 (spt, J=6.8 Hz, 1H), 1.29 ppm (d, J=6.8 Hz, 6H).

[0969] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=156.5, 146.2, 127.2, 123.6, 34.2, 23.5 ppm.

[0970] HRMS (TOF-EI) m/z calculated for C.sub.9H.sub.12NO.sub.2 166.0868 [M+H].sup.+, found 166.0862.

[0971] The NMR data is in agreement with the data in the literature (C. Han, S. L. Buchwald, J. Am. Chem. Soc. 2009, 131, 7532-7533).

e) 4-isopropyl-N,N-dimethylaniline [CAS: 4139-78-0]

[0972] ##STR00117## [0973] Catalyst/Pd source: 1 mol % 7-Br [0974] Aryl chloride: 79.4 mg of 4-chloroaniline [0975] Boronic acid: 65.9 mg of isopropylboronic acid [0976] Yield: 73.2 mg (82%) brown liquid.

[0977] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.89 (d, J=8.8 Hz, 2H), 7.30 (d, J=6.6 Hz, 2H), 2.95 (spt, J=6.9 Hz, 1H), 2.55 (s, 3H), 1.26 ppm (d, J=7.0 Hz, 6H).

[0978] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=149.0, 137.3, 127.0, 113.0, 41.0, 33.1, 24.2 ppm.

[0979] MS (EI) m/z (%) 163.1 (30) [M+], 148.1 (100), 133.1 (8), 120.1 (5),104.0. (4), 91.0 (4), 77.0 (5).

[0980] The NMR data is in agreement with the data in the literature (S. Kanemura, A. Kondoh, H. Yorimitsu, K. Oshima, Synthesis 2008, 2008, 2659-2664).

f) 4-isopropylphenyl-1H-pyrrole [CAS: 166963-93-5]

[0981] ##STR00118## [0982] Catalyst/Pd source: 1 mol % 7-Br [0983] Aryl chloride: 91.6 mg of 1-(4-chlorophenyl)-1H-pyrrole [0984] Boronic acid: 65.9 mg of isopropylboronic acid [0985] Yield: 82.4 mg (89%) colorless liquid.

[0986] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.19-7.24 (m, 4H), 7.00 (t, J=2.2 Hz, 2H), 6.27 (t, J=2.2 Hz, 2H), 2.87 (spt, J=6.9 Hz, 1H), 1.21 ppm (d, J=6.9 Hz, 6H).

[0987] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=146.4, 138.7, 127.5, 120.7, 119.5, 110.0, 33.6, 24.1 ppm.

[0988] MS (EI) m/z (%) 185.1 (62) [M+], 170.0 (100), 153.0 (8), 143.1 (8),128.0. (10), 115.0 (10), 103.0 (3).

[0989] The NMR data is in agreement with the data in the literature (L. Li, S. Zhao, A. Joshi-Pangu, M. Diane, M. R. Biscoe, J. Am. Chem. Soc. 2014, 136, 14027-14030).

g) 4-isopropyltrifluorotoluene [CAS: 32445-99-1]

[0990] ##STR00119## [0991] Catalyst/Pd source: 1 mol % 7-Br [0992] Aryl chloride: 90.3 mg of 4-chlorotrifluorotoluene [0993] Boronic acid: 65.9 mg of isopropylboronic acid [0994] Yield: 92.4 mg (98%) yellow liquid.

[0995] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.60 (d, J=8.1 Hz, 2H), 7.37 (dd, J=8.1, 0.5 Hz, 2H), 3.01 (spt, J=7.0 Hz, 1H), 1.32 ppm (d, J=6.8 Hz, 6H).

[0996] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=152.8, 129.0, 128.2, 126.7, 125.2 (q, J=3.9 Hz), 124.2 (q, J=270.1 Hz), 34.1, 23.7 ppm; .sup.19F NMR (235 MHz, CDCl.sub.3): ?=?62.2 ppm.

[0997] MS (EI) m/z (%) 188.1 (44) [M+], 173.1 (100), 169.1 (11), 159.0 (6),153.0 (24), 133.0 (34), 127.0 (11).

[0998] The NMR data is in agreement with the data in the literature (S. Mizuta, I. S. R. Stenhagen, M. O'Duill, J. Wolstenhulme, A. K. Kirjavainen, S. J. Forsback, M. Tredwell, G. Sandford, P. R. Moore, M. Huiban, S. K. Luthra, J. Passchier, O. Solin, V. Gouverneur, Org. Lett. 2013, 15, 2648-2651).

h) 3-isopropylanisole [CAS: 6380-20-7]

[0999] ##STR00120## [1000] Catalyst/Pd source: 1 mol % 7-Br [1001] Aryl chloride: 72.8 mg of 3-chloroanisole [1002] Boronic acid: 65.9 mg of isopropylboronic acid [1003] Yield: 72.0 mg (96%) colorless liquid.

[1004] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.23 (t, J=7.8 Hz, 1H), 6.71-6.88 (m, 3H), 3.82 (s, 3H), 2.90 (spt, J=6.8 Hz, 1H), 1.26 ppm (d, J=6.8 Hz, 6H).

[1005] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=159.6, 150.6, 129.2, 118.9, 112.4, 110.7, 55.1, 34.2, 23.9 ppm.

[1006] MS (EI) m/z (%) 188.1 (44) [M+], 173.1 (100), 169.1 (11), 159.0 (6),153.0 (24), 133.0 (34), 127.0 (11).

[1007] The NMR data is in agreement with the data in the literature (A. Joshi-Pangu, M. Ganesh, MR Biscoe, Org. Lett. 2011, 13, 1218-1221).

i) Fluoro-3-isopropyltoluene[CAS: 2193-38-6]

[1008] ##STR00121## [1009] Catalyst/Pd source: 1 mol % 7-Br [1010] Aryl chloride: 65.9 mg of 1-chloro-3-fluorobenzene [1011] Boronic acid: 65.9 mg of isopropylboronic acid [1012] Yield: 67.4 mg (98%) colorless liquid.

[1013] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.04-7.14 (m, 1H), 6.98 (d, J=7.7 Hz, 1H), 6.80-6.95 (m, 2H), 2.88 (spt, J=7.0 Hz, 1H), 1.22 ppm (d, J=7.0 Hz, 6H).

[1014] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=164.5 (d, J=244.4 Hz), 137.8, 129.6 (d, J=8.3 Hz), 124.5 (d, J=3.3 Hz), 116.3 (d, J=24.4 Hz), 112.5 (d, J=21.0 Hz), 33.9, 23.8 ppm.

[1015] .sup.19F-NMR (235 MHz, CDCl.sub.3) ?=?113.7 ppm.

[1016] MS (EI) m/z (%) 138.1 (38) [M+], 123.0 (100), 109.0 (8), 103.0 (41), 96.0 (7), 83.0 (3), 77.0 (8).

[1017] The NMR data is in agreement with the data in the literature (T. Kr?ger, K. Vorndran, T. Linker, Chem. Eur. J. 2009, 15, 12082-12091).

j) Cumene [CAS: 98-82-8]

[1018] ##STR00122## [1019] Catalyst/Pd source: 1 mol % 7-Br [1020] Aryl chloride: 56.6 mg of chlorobenzene [1021] Boronic acid: 65.9 mg of isopropylboronic acid [1022] Yield: 57.2 mg (95%) colorless liquid.

[1023] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.19-7.37 (m, 5H), 2.94 (d, J=7.0 Hz, 1H), 1.29 ppm (d, J=7.1 Hz, 6H).

[1024] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=148.8, 128.3, 126.4, 125.7, 34.1, 24.0 ppm.

[1025] HRMS (TOF-EI) m/z calculated for C.sub.9H.sub.12 119.0859 [M?H].sup.+; found 119.0857.

[1026] The NMR data is in agreement with the data in the literature (G. Cahiez, L. Foulgoc, A. Moyeux, Angewandte Chemie International Edition 2009, 48, 2969-2972).

k) 2-isopropyltoluene [CAS: 527-84-4]

[1027] ##STR00123## [1028] Catalyst/Pd source: 1 mol % 7-Br [1029] Aryl chloride: 64.6 mg of 4-chlorotoluene [1030] Boronic acid: 65.9 mg of isopropylboronic acid [1031] Yield: 64.2 mg (96%) colorless liquid.

[1032] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.05-7.26 (m, 4H), 3.15 (spt, J=6.9 Hz, 1H), 2.35 (s, 3H), 1.24 ppm (d, J=7.0 Hz, 6H).

[1033] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=146.8, 134.9, 130.2, 126.2, 125.5, 124.6, 29.2, 23.2, 19.3 ppm.

[1034] MS (EI) m/z (%) 134.1 (32) [M+], 119.0 (100), 103.0 (4), 93.1 (2), 91.0 (20), 77.0 (6), 65.0 (5).

[1035] The NMR data is in agreement with the data in the literature (T. Kr?ger, K. Vorndran, T. Linker, Chem. Eur. J. 2009, 15, 12082-12091).

l) Fluoro-2-isopropylbenzene [CAS: 2022-67-5]

[1036] ##STR00124## [1037] Catalyst/Pd source: 1 mol % 7-Br [1038] Aryl chloride: 65.2 mg of chloro-2-fluorobenzene [1039] Boronic acid: 65.9 mg of isopropylboronic acid [1040] Yield: 67.8 mg (98%) yellow liquid.

[1041] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=6.86-7.19 (m, 4H), 3.08-3.23 (spt, J=7.0 Hz, 1H), 1.17 ppm (d, J=7.0 Hz, 6H).

[1042] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=60.7 (d, J=245.5 Hz), 135.3 (d, J=14.4 Hz), 127.1 (m), 124.0 (d, J=3.9 Hz), 115.2 (d, J=23.2 Hz), 27.1(d, J=2.2 Hz), 22.6 ppm.

[1043] .sup.19F-NMR (235 MHz, CDCl.sub.3) ?=?119.3 ppm.

[1044] IR (ATR): {tilde over (v)}=2965 (w), 2932 (vw), 2872 (vw), 1580(w), 1490 (m), 1454 (w), 1230 (m), 1185 (w), 1085 (w), 1025 (w), 893 (w), 819 (m), 751 (s), 747 (w), 650 (vw), 614 (w), 542 cm.sup.?1 (w).

[1045] HRMS (TOF-EI) m/z calculated for C.sub.10H.sub.14O 124.0688 [M?Me].sup.+, found 124.0648. [1046] m) Isopropyl-3,5-dimethoxybenzene [CAS: 73109-76-9]

##STR00125## [1047] Catalyst/Pd source: 1 mol % 7-Br [1048] Aryl chloride: 89.0 mg of 4-chloroanisole [1049] Boronic acid: 65.9 mg of isopropylboronic acid [1050] Yield: 81.4 mg (90%) colorless liquid.

[1051] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=6.42 (dd, J=2.4, 0.4 Hz, 2H), 6.32 (t, J=2.2 Hz, 1H), 3.81 (s, 6H), 2.86 (spt, J=6.8 Hz, 1H), 1.26 ppm (d, J=6.8 Hz, 6H).

[1052] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=160.7, 151.5, 104.6, 97.4, 55.2, 34.4, 23.9 ppm.

[1053] MS (EI) m/z (%) 180.1 (77) [M+], 165.1 (100), 152.1 (48), 135.1 (7), 121.0 (7), 105.0 (16), 91.0 (13).

[1054] The NMR data is in agreement with the data in the literature (I. Y. EI-Deeb, T. Funakoshi, Y. Shimomoto, R. Matsubara, M. Hayashi, J. Org. Chem. 2017, 82, 2630-2640).

n) Isopropyl-2,6-dimethylbenzene [CAS: 14411-75-7]

[1055] ##STR00126## [1056] Catalyst/Pd source: 1 mol % 7-Br [1057] Aryl chloride: 71.8 mg of 2-chloro-m-xylene [1058] Boronic acid: 65.9 mg of isopropylboronic acid [1059] Yield: 68.6 mg (93%) colorless liquid.

[1060] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=6.88 (m, 3H), 3.35 (spt, J=7.0 Hz, 1H), 2.30 (s, 6H), 1.25 ppm (d, J=7.0 Hz, 6H).

[1061] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=144.1, 136.1, 128.0, 125.4, 29.5, 21.5, 20.8 ppm.

[1062] MS (EI) m/z (%) 148.1 (24) [M+], 133.1 (2), 119.1 (100), 115.0 (5), 103.0 (3), 91.0 (10), 77.0 (5).

[1063] The NMR data is in agreement with the data in the literature (T. Si, B. Li, W. Xiong, B. Xu, W. Tang, Org. Biomol. Chem. 2017, 15, 9903-9909).

o) 5-isopropyl-3-methyl[b]benzothiophene [CAS: 18272-84-9]

[1064] ##STR00127## [1065] Catalyst/Pd source: 1 mol % 7-Br [1066] Aryl chloride: 94.2 mg of 5-isopropyl-3-methylbenzo[b]thiophene [1067] Boronic acid: 65.9 mg of isopropylboronic acid [1068] Yield: 76.4 mg (80%) white solid.

[1069] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.79 (d, J=8.3 Hz, 1H), 7.58 (s, 1H), 7.28 (dd, J=8.3, 1.2 Hz, 1H), 7.07 (s, 1H), 3.09 (spt, J=6.8 Hz, 1H), 2.47 (d, J=1.1 Hz, 3H), 1.36 ppm (d, J=6.8 Hz, 6H).

[1070] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=145.3, 140.2, 138.2, 132.4, 123.8, 122.9, 122.0, 119.4, 34.7, 24.8, 14.3 ppm.

[1071] HRMS (TOF-EI) m/z calculated for C.sub.12H.sub.14S 190.0816 [M].sup.+; found 190.0807.

[1072] The NMR data is in agreement with the data in the literature (L. Li, S. Zhao, A. Joshi-Pangu, M. Diane, M. R. Biscoe, J. Am. Chem. Soc. 2014, 136, 14027-14030).

p) 4-butylanisole [CAS: 18272-84-9]

[1073] ##STR00128## [1074] Catalyst/Pd source: 1 mol % 7-Br [1075] Aryl chloride: 72.7 mg of 4-chloroanisole [1076] Boronic acid: 79.6 mg of n-butylboronic acid [1077] Yield: 63.7 mg (78%) colorless liquid.

[1078] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.14 (d, J=7.8 Hz, 2H), 6.87 (d, J=7.8 Hz, 2H), 3.82 (s, 3H), 2.59 (t, J=7.8 Hz, 2H), 1.61 (dt, J=7.8, 7.3 Hz, 2H), 1.39 (dq, J=7.8, 7.3 Hz, 2H), 0.96 ppm (t, J=7.3 Hz, 3H).

[1079] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.6, 135.0, 129.2, 113.6, 55.2, 34,7, 33.9, 22.3, 14.0 ppm.

[1080] MS (EI) m/z (%) 164.1 (19) [M+], 121.1 (100), 103.0 (1), 91.0 (6), 77.0 (6), 65.0 (3).

[1081] The NMR data is in agreement with the data in the literature (G. Cahiez, L. Foulgoc, A. Moyeux, Angewandte Chemie International Edition 2009, 48, 2969-2972).

q) 4-isobutylanisole [CAS: 91967-52-1]

[1082] ##STR00129## [1083] Catalyst/Pd source: 1 mol % 7-Br [1084] Aryl chloride: 72.7 mg of 4-chloroanisole [1085] Boronic acid: 80.5 mg of isobutylboronic acid [1086] Yield: 67.3 mg (82%) colorless liquid.

[1087] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.07 (d, J=8.6 Hz, 2H), 6.84 (d, J=8.6 Hz, 2H), 3.80 (s, 3H), 2.43 (d, J=7.2 Hz, 2H), 1.82 (spt, J=6.8 Hz, 1H), 0.91 ppm (s, 6H).

[1088] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.6, 133.8, 130.0, 113.5, 55.2, 44.5, 30.4, 22.7 ppm.

[1089] MS (EI) m/z (%) 164.1 (25) [M+], 149.1 (1), 121.1 (100), 115.0 (2), 91.0 (6), 77.0 (7), 65.0 (2).

[1090] The NMR data is in agreement with the data in the literature (S. D. Dreher, S.-E. Lim, D. L. Sandrock, G. A. Molander, J. Org. Chem. 2009, 74, 3626-3631).

r) 4-sec-butylanisole [CAS: 4917-90-2]

[1091] ##STR00130## [1092] Catalyst/Pd source: 1 mol % 7-Br [1093] Aryl chloride: 72.7 mg of 4-chloroanisole [1094] Boronic acid: 76.5 mg of sec-butylboronic acid [1095] Yield: 64.5 mg (79%) colorless liquid.

[1096] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.11 (d, J=7.8 Hz, 2H), 6.86 (d, J=7.8 Hz, 2H), 3.81 (s, 3H), 2.51-2.66 (m, 1H), 1.54-1.63 (m, 2H), 1.23 (d, J=7.3 Hz, 3H), 0.83 ppm (t, J=7.3 Hz, 3H).

[1097] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.6, 139.8, 127.8, 113.6, 65.8, 55.2, 40.8, 31.3, 22.0, 12.2 ppm.

[1098] MS (EI) m/z (%) 164.1 (21) [M+], 149.1 (5), 135.1 (100), 121.0 (9), 105.0 (13), 91.0 (10), 77.0 (6).

[1099] The NMR data is in agreement with the data in the literature (L. Li, S. Zhao, A. Joshi-Pangu, M. Diane, M. R. Biscoe, J. Am. Chem. Soc. 2014, 136, 14027-14030).

s) 4-octylanisole [CAS: 3307-19-5]

[1100] ##STR00131## [1101] Catalyst/Pd source: 1 mol % 7-Br [1102] Aryl chloride: 72.7 mg of 4-chloroanisole [1103] Boronic acid: 119 mg of octylboronic acid [1104] Yield: 90.2 mg (82%) colorless liquid.

[1105] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.15 (d, J=8.7 Hz, 2H), 6.73 (d, J=8.7 Hz, 2H), 3.68 (s, 3H), 2.38-2.53 (m, 2H), 1.48 (quin, J=7.8 Hz, 2H), 1.10-1.34 (m, 10H), 0.79 ppm (t, J=6.9 Hz, 3H).

[1106] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.6, 135.0, 129.3, 113.6, 55.4, 35.0, 31.9, 31.7, 29.5, 29.3, 22.6, 14.1 ppm.

[1107] MS (EI) m/z (%) 220.2 (13) [M+], 121.0 (100), 91.0 (4), 77.0 (4).

[1108] The NMR data is in agreement with the data in the literature (G. Cahiez, C. Chaboche, C. Duplais, A. Moyeux, Org. Lett. 2009, 11, 277-280).

t) 4-cyclopropylanisole [CAS:4030-17-5]

[1109] ##STR00132## [1110] Catalyst/Pd source: 1 mol % 7-Br [1111] Aryl chloride: 72.7 mg of 4-chloroanisole [1112] Boronic acid: 67.1 mg of cyclopropylboronic acid [1113] Yield: 71.8 mg (97%) colorless liquid.

[1114] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.00-7.10 (m, 2H), 6.79-6.89 (m, 2H), 3.81 (s, 3H), 1.79-1.99 (m, 1H), 0.89-0.97 (m, 2H), 0.57-0.71 ppm (m, 2H).

[1115] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.5, 135.8, 126.8, 113.7, 55.2, 14.6, 8.5 ppm.

[1116] MS (EI) m/z (%) 148.1 (100) [M+], 133.0 (26), 117.1 (38), 105.0 (22), 91.0 (19), 77.0 (27), 63.0 (6).

[1117] The NMR data is in agreement with the data in the literature (G. A. Molander, P. E. Gormisky, J. Org. Chem. 2008, 73, 7481-7485).

u) 4-cyclobutylanisole [CAS:39868-68-3]

[1118] ##STR00133## [1119] Catalyst/Pd source: 1 mol % 7-Br [1120] Aryl chloride: 72.7 mg of 4-chloroanisole [1121] Boronic acid: 78.9 mg of cyclobutylboronic acid [1122] Yield: 62.1 mg (77%) pale yellow solid.

[1123] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.07 (d, J=8.3 Hz, 2H), 6.76 (d, J=8.3 Hz, 2H), 3.72-3.74 (m, 1H), 3.71 (s, 3H), 2.18-2.30 (m, 2H), 1.96-2.08 (m, 2H), 1.80-1.94 (m, 1H), 1.72-1.77 ppm (m, 1H).

[1124] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.7, 127.2, 113.6, 55.3, 39.8, 30.1, 18.2 ppm.

[1125] MS (EI) m/z (%) 162.1 (19) [M+], 134.0 (100), 131.1 (2), 119.0 (23), 115.0 (2), 91.0 (15), 77.0 (4).

[1126] The NMR data is in agreement with the data in the literature (P. C. Too, G. H. Chan, Y. L. Tnay, H. Hirao, S. Chiba, Angew. Chem. Int. Ed. 2016, 55, 3719-3723).

v) 4-cyclopentylanisole [CAS:1507-97-7]

[1127] ##STR00134## [1128] Catalyst/Pd source: 1 mol % 7-Br [1129] Aryl chloride: 72.7 mg of 4-chloroanisole [1130] Boronic acid: 88.1 mg of cyclopentylboronic acid [1131] Yield: 57.3 mg (65%) colorless liquid.

[1132] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.02 (d, J=8.0 Hz, 2H), 6.69 (d, J=7.7 Hz, 2H), 3.63 (s, 3H), 2.71-2.88 (m, 1H), 1.82-1.99 (m, 2H), 1.32-1.71 ppm (m, 6H).

[1133] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.6, 138.4, 127.8, 113.5, 55.1, 45.1, 34.6, 25.3 ppm.

[1134] MS (EI) m/z (%) 176.1 (59) [M+], 161.1 (6), 147.1 (100), 134.0 (29), 129.0 (29), 121.0 (33), 115.0 (9).

[1135] The NMR data is in agreement with the data in the literature (S. D. Dreher, P. G. Dormer, D. L. Sandrock, G. A. Molander, J. Am. Chem. Soc. 2008, 130, 9257-9259).

w) 4-cyclohexylanisole [CAS:613-36-5]

[1136] ##STR00135## [1137] Catalyst/Pd source: 1 mol % 7-Br [1138] Aryl chloride: 72.7 mg of 4-chloroanisole [1139] Boronic acid: 99.0 mg of cyclohexylboronic acid [1140] Yield: 75.6 mg (80%) pale yellow crystals.

[1141] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.17 (d, J=8.4 Hz, 2H), 6.88 (d, J=8.4 Hz, 2H), 3.82 (s, 3H), 2.43-2.56 (m, 1H), 1.84-1.93 (m, 4H), 1.74-1.82 (m, 1H), 1.38-1.51 (m, 4H), 1.18-1.37 ppm (m, 1H).

[1142] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.6, 140.3, 127.6, 113.6, 55.2, 43.7, 34.7, 26.9, 26.2 ppm.

[1143] MS (EI) m/z (%) 190.1 (70) [M+], 147.1 (100), 134.0 (22), 121.0 (40), 115.0 (7), 91.0 (18), 77.0 (6).

[1144] The NMR data is in agreement with the data in the literature (P. C. Too, G. H. Chan, Y. L. Tnay, H. Hirao, S. Chiba, Angew. Chem. Int. Ed. 2016, 55, 3719-3723).

C. Suzuki-Miyaura Cross-Coupling of Sterically Hindered Substrates

[1145] The above-mentioned palladium-naphthyl catalysts (7-8 Cl/Br) were also tested for activity in room-temperature Suzuki-Miyaura couplings of aryl chlorides which lead to the formation of extremely sterically shielded tetra-ortho-substituted compounds.

General Procedure for Suzuki-Miyaura Cross-Coupling of Sterically Hindered Substrates

[1146] A vial was filled with the respective catalyst (0.005 mol, 0.01 eq.) in the absence of air and transferred to the glove box. 4.72 mg of the ligand IPr*OMe, (0.01 mmol, 0.02 eq. CAS: 1416368-06-3), 66 mg of KOH (1.0 mmol, 2.0 eq.) and the boronic acid (0.75 mmol, 1.5 eq.) were weighed out and the vial was sealed. A solution of the aryl chloride (0.5 mmol, 1.0 eq.) and 30 ?l of n-tetradecane in 2 ml of THE was added using a syringe. The resulting homogeneous solution was stirred for 12 hours at room temperature. After completion of the reaction, the mixture was diluted with EtOAc (10 ml) and washed with water (2?10 ml). The combined organic phases were dried over MgSO.sub.4, filtered, and the volatile components were removed under reduced pressure. The residue was purified by flash column chromatography (SiO2, cyclohexane), giving the corresponding biphenyl.

[1147] The coupling of 2-chloro-m-xylene with 2,4,6-trimethylphenylboronic acid was chosen as model reaction. The various Pd sources were investigated under the conditions described by Nolan (A. Chartoire, M. Lesieur, L. Falivene, A. M. Z. Slawin, L. Cavallo, C. S. J. Cazin, S. P. Nolan, Chem. Eur. J. 2012, 18, 4517-4521; G. Bastug, S. P. Nolan, Organometallics 2014, 33, 1253-1258). Nolan's protocol is based on the electron-rich, highly sterically demanding NHC ligand IPr*OMe in combination with [Pd(cinnamyl)Cl]2 and has achieved record highs in this regard. The only adjustment made here to Nolan's protocol was the use of THE instead of DME (1,2-dimethoxyethane) as solvent, due to the low solubility of the dimeric palladium-naphthyl catalysts in DME.

Model Reaction Preparation of 2,2,4,6,6-pentamethylbiphenyl [CAS: 76411-12-6]

[1148] ##STR00136## [1149] Catalyst/Pd source: 0.5 mol % 7-Cl or 7-Br or 8-Cl or 8-Br or 0.5 mol % [1150] [Pd(cinnamyl)Cl].sub.2* [1151] Aryl chloride: 71.7 mg of 2-chloro-m-xylene [1152] Boronic acid: 123.0 mg of 2,4,6-trimethylboronic acid [1153] * for comparative purposes

TABLE-US-00024 TABLE B-4 Use in the Suzuki-Miyaura coupling of sterically hindered substrates using the example of the preparation of 2,2,4,6,6- pentamethylbiphenyl Entry Catalyst Yield [%].sup.a) 1 7-Cl >99 2 7-Br >99 3 8-Cl >99 4 8-Br >99 .sup.a)Yields determined by GC analysis with n-tetradecane as internal standard

[1154] With all four palladium-naphthyl catalysts (7-8 Cl/Br) in combination with the NHC ligand IPr*OMe, the desired product was formed in a quantitative yield within 12 h at room temperature under the reaction conditions given above. In comparison, the use of [Pd(cinnamyl)Cl]2 and the NHC ligand IPr*OMe, with DME chosen as the solvent, led to a 95% yield of the expected biaryl compound after a reaction time of 22 hours at room temperature. Consequently, the four palladium-naphthyl catalysts (7-8 Cl/Br) performed well compared to the catalyst precursor described by Nolan.

[1155] Analytical data from 2,2,4,6,6-pentamethylbiphenyl prepared using 7-Br:

[1156] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.08-7.22 (m, 3H), 6.99 (s, 2H), 2.38 (s, 3H), 1.94 (s, 6H), 1.90 ppm (s, 6H).

[1157] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=140.0, 136.9, 136.1, 135.7, 135.2, 128.2, 127.3, 126.7, 21.1, 19.9, 19.7 ppm.

[1158] MS (EI) m/z (%) 224.1 (70) [M+], 209.1 (100), 194.0 (39), 188.9 (7), 179.0 (34), 165.0 (12), 152.9 (6).

[1159] The NMR data is in agreement with the data in the literature (A. Chartoire, M. Lesieur, L. Falivene, A. M. Z. Slawin, L. Cavallo, C. S. J. Cazin, S. P. Nolan, Chem. Eur. J. 2012, 18, 4517-4521).

[1160] Further examples for Suzuki-Miyaura cross-coupling of sterically hindered substrates

a) 2,6-dimethoxy-2,4,6-trimethylbiphenyl [CAS: 471290-69-4]

[1161] ##STR00137## [1162] Catalyst/Pd source: 0.5 mol % 7-Br [1163] Aryl chloride: 88.1 mg of 2-chloro-1,3-dimethoxybenzene [1164] Boronic acid: 123.0 mg of 2,4,6-trimethylboronic acid [1165] Yield: 126 mg (97%) off-white solid.

[1166] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.28-7.36 (m, 1H), 6.91-6.99 (s, 2H), 6.62-6.71 (m, 2H), 3.70-3.77 (s, 6H), 2.31-2.37 (s, 3H), 1.94-2.02 ppm (s, 6H).

[1167] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=157.7, 136.9, 136.3, 130.9, 135.2, 128.5, 127.9, 117.7, 103.9, 55.8, 21.3, 20.3 ppm.

[1168] MS (EI) m/z (%) 224.1 (70) [M+], 209.1 (100), 194.0 (39), 188.9 (7), 179.0 (34), 165.0 (12), 152.9 (6).

[1169] The NMR data is in agreement with the data in the literature (A. Chartoire, M. Lesieur, L. Falivene, A. M. Z. Slawin, L. Cavallo, C. S. J. Cazin, S. P. Nolan, Chem. Eur. J. 2012, 18, 4517-4521).

b) 1-(2,6-dimethylphenyl)naphthalene [CAS: 471290-69-4]

[1170] ##STR00138## [1171] Catalyst/Pd source: 0.5 mol % 7-Br [1172] Aryl chloride: 71.7 mg of 2-chloro-m-xylene [1173] Boronic acid: 136.0 mg of 1-naphthylboronic acid [1174] Yield: 114 mg (98%) off-white solid.

[1175] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.75-7.86 (m, 2H), 7.35-7.51 (m, 2H), 7.08-7.28 (m, 6H), 1.83 ppm (s, 6H).

[1176] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=139.6, 138.7, 137.0, 133.7, 131.7, 128.3, 127.3, 127.2, 126.4, 126.0, 125.8, 125.7, 125.4, 20.4 ppm.

[1177] MS (EI) m/z (%) 232.1 (100) [M+], 226.1 (4), 217.1 (89), 202.1 (30), 189.1 (7), 176.0 (2), 165.1 (3).

[1178] The NMR data is in agreement with the data in the literature (B. H. Lipshutz, T. B. Petersen, A. R. Abela, Org. Lett. 2008, 10, 1333-1336).

3.2 Test of the Dimeric Allylpalladium Halide Complexes According to General Formula VIII in Buchwald-Hartwig Couplings, Heck Reactions, ?-Arylation of Ketones and Negishi Couplings

[1179] The allylpalladium halide phosphine complexes were produced in situ.

A. General Procedure for Buchwald-Hartwig Aminations

[1180] A vial was filled with the catalyst (0.005 mmol, 0.005 eq.) and the ligand RuPhos (0.01 mmol, 0.01 eq.) in the absence of air and then transferred to the glove box, where 1 ml of THE was added. The resulting homogeneous solution was stirred for 20 minutes at room temperature. Thereafter, a solution of aryl chloride (1.0 mmol, 1 eq.), amine (1.1 mmol, 1.1 eq.), 168 mg of potassium tert-butoxide (1.5 mmol, 1.5 eq.) and 50 ?l of n-undecane (0.191 mmol, 0.191 eq.) in 1 ml of THE was added to the catalyst solution. The vial was then capped and the reaction stirred for 12 hours at room temperature outside the glove box. After completion of the reaction, it was diluted with EtOAc (10 ml) and washed with water (2?10 ml). The combined organic phases were dried over MgSO.sub.4, filtered and the volatile components removed under reduced pressure. The residue was purified by column chromatography (SiO2, cyclohexane), giving the corresponding amine.

[1181] As a model reaction, the preparation of N-tert-butyl-2,6-dimethylaniline [CAS: 395116-77-5] was chosen:

##STR00139## [1182] Catalyst/Pd source: 0.5 mol % 7-Cl or 7-Br or 8-Cl or 8-Br or 0.5 mol % [Pd(tBu-indenyl)Cl].sub.2* [1183] Aryl chloride: 143 mg of 2,6-dimethylphenyl chloride [1184] Amine: 82.1 mg of N-tert-butylamine [1185] * for comparative purposes

TABLE-US-00025 TABLE B-5 Use in Buchwald-Hartwig amination using the example of the preparation of N-tert-butyl-2,6-dimethylaniline Entry Catalyst Yield [%].sup.a) 1 7-Cl >99 2 7-Br >99 3 8-Cl 88 4 8-Br 82 .sup.a)Yields determined by GC analysis with n-undecane as internal standard.

[1186] With all four palladium-naphthyl catalysts (7-8 Cl/Br) in combination with the phosphine ligand RuPhos, the desired product was formed at a good to excellent yield under the reaction conditions given above. Under the above-mentioned reaction conditions, catalysts 7-Cl and 7-Br (substitution in the 1-position) were equally reactive and showed higher activity than catalysts 8-Cl and 8-Br (substitution in the 2-position). In comparison, the use of the Hazari catalyst [Pd(t-Bu-indenyl)Cl]2 and of the phosphine ligand RuPhos under otherwise identical reaction conditions led to a 93% yield of the expected compound. Consequently, the two palladium-naphthyl catalysts 7-Cl and 7-Br performed better than the Hazari catalyst.

[1187] Analytical data from N-tert-butyl-2,6-dimethylaniline prepared using 7-Br:

[1188] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.02-7.07 (m, 2H), 6.93 (d, J=7.3 Hz, 1H), 2.36 (s, 6H), 1.23 ppm (s, 9H).

[1189] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=144.0, 134.8, 128.6, 123.2, 55.3, 31.2, 20.4 ppm.

[1190] MS (EI) m/z (%) 177.1 (34) [M+], 162.1 (62), 121.0 (100), 106.1 (43), 91.0 (14), 77.0 (14), 57.1 (13).

[1191] The NMR data is in agreement with the data in the literature (W. I. Lai, M. P. Leung, P. Y. Choy, F. Y. Kwong, Synthesis 2019, 51, 2678-2686).

[1192] Further examples for Buchwald-Hartwig aminations a) N,N-dibutyl-4-toluidine [CAS: 31144-33-9]

##STR00140## [1193] Catalyst/Pd source: 0.5 mol % 7-Br [1194] Aryl chloride: 129 mg of 4-chlorotoluene [1195] Amine: 142 mg of N,N-dibutylamine [1196] Yield: 216 mg (99%) colorless liquid.

[1197] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.07 (d, J=8.3 Hz, 2H), 6.63 (d, J=8.4 Hz, 2H), 3.23-3.33 (m, 4H), 2.29 (s, 3H), 1.53-1.66 (m, 4H), 1.31-1.47 (m, 4H), 1.00 ppm (t, J=7.3 Hz, 6H).

[1198] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=146.2, 129.7, 124.3, 112.1, 51.0, 29.4, 20.4, 20.1, 14.0 ppm.

[1199] MS (EI) m/z (%) 291.2 (31) [M+], 176.2 (100), 160.1 (2), 146.1 (1), 134.1 (78), 120.1 (44), 91.1 (20), 77.0 (13).

[1200] The NMR data is in agreement with the data in the literature (R. Pratap, D. Parrish, P. Gunda, D. Venkataraman, M. K. Lakshman, J. Am. Chem. Soc. 2009, 131, 12240-12249).

b)N-butyl-2,6-dimethylaniline [41115-22-4]

[1201] ##STR00141## [1202] Catalyst/Pd source: 0.5 mol % 7-Br [1203] Aryl chloride: 143 mg of 2,6-dimethylphenyl chloride [1204] Amine: 80.5 mg of N-butylamine [1205] Yield: 172 mg (97%) yellow liquid.

[1206] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.03 (d, J=7.5 Hz, 2H), 6.85 (t, J=7.5 Hz, 1H), 3.03 (t, J=7.5 Hz, 2H), 2.97 (br s, 1H), 2.34 (s, 6H), 1.55-1.70 (m, 2H), 1.47 (sxt, J=7.4 Hz, 2H), 1.00 ppm (t, J=7.5 Hz, 3H).

[1207] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=146.1, 128.7, 128.4, 121.2, 48.0, 33.0, 20.0, 18.2, 13.6 ppm.

[1208] MS (EI) m/z (%) 291.2 (31) [M+], 176.2 (100), 160.1 (2), 146.1 (1), 134.1 (78), 120.1 (44), 91.1 (20), 77.0 (13).

[1209] The NMR data is in agreement with the data in the literature (L. Ackermann, J. H. Spatz, C. J. Gschrei, R. Born, A. Althammer, Angew. Chem. Int. Ed. 2006, 45, 7627-7630).

B. General Procedure for Heck Reactions

[1210] A solution of the catalyst (0.01 mmol, 0.01 eq.) and of the ligand PAd.sub.2nBu (0.02 mmol, 0.02 eq.) in 0.5 ml of dioxane was stirred for 20 minutes at room temperature in the glove box. The stock solution was then added to a vial containing aryl chloride (0.5 mmol, 1 eq), 71 mg of tert-butyl acrylate (0.55 mmol, 1.1 eq) and 461 mg of tetrabutylammonium acetate (1.25 mmol, 2.5 eq) in 1 ml of dioxane. The vials were then capped and stirring was carried out for 16 hours at 120? C. outside the glove box. After completion of the reaction, the vial was opened and the solution was diluted with 3 ml of EtOAc. The reaction solution was filtered using a pipette containing MgSO.sub.4 and SiO2. The pipette was washed with more EtOAc until the filtrate became colorless. The solvent was removed under reduced pressure and the sample was purified by flash column chromatography (SiO2, cyclohexane/EtOAc 0%.fwdarw.20%) to obtain the desired product.

[1211] The preparation of tert-butyl-3-(3-quinolinyl)acrylate [CAS: 259232-14-9] was chosen as model reaction:

##STR00142## [1212] Catalyst/Pd source: 1 mol % 7-Cl or 7-Br or 8-Cl or 8-Br or 1 mol % [Pd(tBu-indenyl)Cl].sub.2* [1213] Aryl chloride: 82.6 mg of 2-chloroquinoline [1214] Yield: 110 mg (86%) yellow solid. [1215] * for comparative purposes

TABLE-US-00026 TABLE B-6 Use in the Heck reaction using the example of the preparation of tert-butyl-3-(3-quinolinyl)acrylate Entry Catalyst Yield [%].sup.a) 1 7-Cl 92 2 7-Br 98 3 8-Cl 84 4 8-Br 98 .sup.a)Yields were determined by GC analysis using n-undecane as internal standard.

[1216] With all four palladium-naphthyl catalysts (7-8 Cl/Br) in combination with the phosphine ligand PAd.sub.2nBu, the desired product was formed at a good to very good yield under the reaction conditions given above. Under the above-mentioned reaction conditions, catalysts 7-Br and 8-Br were equally reactive and showed higher activity than catalysts 7-Cl and 8-Cl. In comparison, the use of the Hazari catalyst [Pd(t-Bu-indenyl)Cl]2 and of the phosphine ligand PAd.sub.2nBu under otherwise identical reaction conditions led to a 95% yield of the expected compound. Consequently, the two palladium-naphthyl catalysts 7-Br and 8-Br performed somewhat better than the Hazari catalyst.

[1217] Analytical data from tert-butyl-3-(3-quinolinyl)acrylate prepared using 7-Br:

[1218] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=8.17 (d, J=7.7 Hz, 1H), 8.10 (d, J=8.5 Hz, 1H), 7.77-7.84 (m, 2H), 7.73 (ddd, J=8.5, 6.9, 1.5 Hz, 1H), 7.61 (d, J=8.5 Hz, 1H), 7.52-7.59 (m, 1H), 6.89 (d, J=15.9 Hz, 1H), 1.56 ppm (s, 9H).

[1219] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=166.5, 154.4, 149.1, 144.1, 137.9, 130.4, 130.0, 128.3, 127.9, 127.5, 126.3, 120.5, 81.8, 29.4 ppm.

[1220] HRMS (ESI) m/z calculated for C.sub.16H.sub.17NO.sub.2 [M+H].sup.+ 256.1338, found 256.1328.

[1221] The NMR data is in agreement with the data in the literature (H. Xia, Y. Liu, P. Zhao, S. Gou, J. Wang, Org. Lett. 2016, 18, 1796-1799).

Further Examples for Heck Reactions

a) tert-butyl-3-(2-methoxyphenyl)acrylate [CAS: 1313193-50-8]

[1222] ##STR00143## [1223] Catalyst/Pd source: 1 mol % 7-Br [1224] Aryl chloride: 72.7 mg of 2-chloroanisole [1225] Yield: 106 mg (91%) yellow liquid.

[1226] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.91 (d, J=16.1 Hz, 1H), 7.49 (dd, J=7.7, 1.7 Hz, 1H), 7.29-7.37 (m, 1H), 6.86-6.99 (m, 2H), 6.44 (d, J=16.1 Hz, 1H), 3.88 (s, 3H), 1.55 (s, 9H) ppm.

[1227] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=164.6, 156.0, 136.6, 128.8, 126.5, 121.4, 118.3, 108.7, 77.9, 53.1, 25.9 ppm.

[1228] HRMS (ESI) m/z calculated for C.sub.14H.sub.18O.sub.3 [M+Na].sup.+ 257.1154, found 257.1142.

[1229] The NMR data is in agreement with the data in the literature (M. Lautens, J. Mancuso, H. Grover, Synthesis 2004, 2004, 2006-2014).

b) tert-butyl-3-(3,5-dimethoxyphenyl)acrylate [CAS: 951174-15-5]

[1230] ##STR00144## [1231] Catalyst/Pd source: 1 mol % 7-Br [1232] Aryl chloride: 89.0 mg of 3,5-dimethoxychlorobenzene [1233] Yield: 124 mg (94%) yellow liquid.

[1234] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.50 (d, J=15.9 Hz, 1H), 6.65 (d, J=2.2 Hz, 2H), 6.47 (t, J=2.3 Hz, 1H), 6.33 (d, J=15.9 Hz, 1H), 3.81 (s, 6H), 1.53 (s, 9H) ppm.

[1235] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=166.2, 161.0, 143.6, 136.6, 120.7, 105.8, 102.3, 80.6, 55.4, 28.2 ppm.

[1236] HRMS (ESI) m/z calculated for C.sub.15H.sub.20O.sub.4 [M+H].sup.+ 265.1440, found 265.1434.

[1237] The NMR data is in agreement with the data in the literature (S. G. Davies, A. W. Mulvaney, A. J. Russell, A. D. Smith, Tetrahedron: Asymmetry 2007, 18, 1554-1566).

c) tert-butyl-3-(2,6-dimethylphenyl)acrylate [CAS: 780761-47-9]

[1238] ##STR00145## [1239] Catalyst/Pd source: 1 mol % 7-Br [1240] Aryl chloride: 71.7 mg of 2-chloro-m-xylene [1241] Yield: 111 mg (96%) off-white solid.

[1242] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.74 (d, J=16.3 Hz, 1H), 7.01-7.17 (m, 3H), 5.99 (d, J=16.3 Hz, 1H), 2.35 (s, 6H), 1.55 (s, 9H) ppm.

[1243] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=166.3, 142.3, 136.8, 134.3, 128.3, 128.2, 125.8, 80.7, 28.4, 21.2 ppm

[1244] HRMS (ESI) m/z calculated for C.sub.15H.sub.20O.sub.2 [M+Na].sup.+ 255.1361, found 255.1352.

[1245] The NMR data is in agreement with the data in the literature (Q. Gao, Y. Shang, F. Song, J. Ye, Z.-S. Liu, L. Li, H.-G. Cheng, Q. Zhou, J. Am. Chem. Soc. 2019, 141, 15986-15993).

d) tert-butyl-3-(2,6-dimethoxyphenyl)acrylate [CAS: 1478401-14-7]

[1246] ##STR00146## [1247] Catalyst/Pd source: 1 mol % 7-Br [1248] Aryl chloride: 88.1 mg of 2,6-dimethoxychlorobenzene [1249] Yield: 110 mg (83%) yellow oil.

[1250] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=8.09 (d, J=16.3 Hz, 1H), 7.27-7.31 (m, 1H), 6.82 (d, J=16.3 Hz, 1H), 6.59 (d, J=8.4 Hz, 2H), 3.91 (s, 6H), 1.57 (s, 9H) ppm.

[1251] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=168.2, 160.1, 134.5, 130.9, 122.7, 112.6, 103.8, 79.9, 55.9, 28.4 ppm.

[1252] IR (ATR): 3001(w), 2958 (w), 2929 (w), 2835 (w), 1589 (s), 1472 (s), 1429 (s), 1299 (w), 1280 (w), 1244 (vs), 1171 (w), 1105 (vs), 1070 (w), 1036 (w), 1008 (w), 898 (w), 785 (w), 761 (w), 725 (w), 698 (s), 655 (w) cm-1.

[1253] HRMS (ESI) m/z calculated for C.sub.15H.sub.20O.sub.4 [M+H].sup.+ 265.1440, found 265.1436.

e) tert-butyl-3-(2-formylphenyl)acrylate [CAS: 103890-69-3]

[1254] ##STR00147## [1255] Catalyst/Pd source: 1 mol % 7-Br [1256] Aryl chloride: 71.0 mg of 2-chlorobenzaldehyde [1257] Yield: 111 mg (96%) pale yellow oil.

[1258] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=10.33 (s, 1H), 8.41 (d, J=15.8 Hz, 1H), 7.82-7.92 (m, 1H), 7.50-7.68 (m, 3H), 6.31 (d, J=15.8 Hz, 1H), 1.55 (s, 9H) ppm.

[1259] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=191.7, 165.5, 139.6, 137.0, 133.9, 131.7, 129.7, 128.0, 125.3, 81.0, 28.2 ppm.

[1260] HRMS (ESI) m/z calculated for C.sub.14H.sub.16O.sub.3 [M+H].sup.+ 233.1177, found 233.1170.

[1261] The NMR data is in agreement with the data in the literature (C. S. Bryan, M. Lautens, Org. Lett. 2010, 12, 2754-2757).

C. General Procedure for the ?-Arylation of Ketones

[1262] A vial was filled with the respective catalyst (0.005 mol, 0.01 eq.) and the ligand RuPhos (0.01 mmol, 0.02 eq.) in the absence of air. After 3 alternating vacuum/argon cycles, 1 ml of THE was added with a syringe. The resulting homogeneous solution was stirred for 10 minutes at room temperature. Then, a solution of aryl chloride (0.5 mmol, 1.0 eq.), ketone (1.0 mmol, 2.0 eq.), 74.3 mg of sodium tert-butoxide (1.5 mmol, 1.5 eq.) and 30 ?l of n-tetradecane (0.116 mmol, 0.232 eq.) in 1 ml of THE was added to the catalyst solution using a syringe. The reaction mixture was stirred for 16 hours at 60? C. After completion of the reaction, the mixture was diluted with EtOAc (10 ml) and washed with saline solution (3?10 ml), then the aqueous phases were extracted with EtOAc (3?10 ml). The combined organic phases were dried over MgSO.sub.4, filtered and the volatile components removed under reduced pressure. The residue was purified by flash column chromatography (SiO.sub.2,cyclohexane/ethyl acetate gradient), giving the corresponding arylated ketone.

[1263] The preparation of 2-(4-methylphenyl)-cyclohexanone [CAS: 52776-14-4] was chosen as model reaction:

##STR00148## [1264] Catalyst/Pd source: 1 mol % 7-Cl or 7-Br or 8-Cl or 8-Br or 1 mol % [Pd(tBu-indenyl)Cl].sub.2* [1265] Aryl chloride: 64.6 mg of 4-chlorotoluene [1266] Ketone: 99.1 mg of cyclohexanone [1267] * for comparative purposes

TABLE-US-00027 TABLE B-7 Use in the Heck reaction using the example of the preparation of 2-(4-methylphenyl)-cyclohexanone Entry Catalyst Yield [%].sup.a) 1 7-Cl 87 2 7-Br 60 3 8-Cl 83 4 8-Br 77 .sup.a)Yields were determined by GC analysis using n-tetradecane as internal standard.

[1268] With all four palladium-naphthyl catalysts (7-8 Cl/Br) in combination with the phosphine ligand RuPhos, the desired product was formed at a good to very good yield under the reaction conditions given above. Under the above-mentioned reaction conditions, catalysts 7-Cl and 8-Cl were approximately equally reactive and showed higher activity than catalysts 7-Br and 8-Br. In comparison, the use of the Hazari catalyst [Pd(t-bu-indenyl)Cl]2 and of the phosphine ligand RuPhos under otherwise identical reaction conditions led to a 75% yield of the expected compound. Consequently, the two palladium-naphthyl catalysts 7-Cl and 8-Cl performed better than the Hazari catalyst.

[1269] Analytical data from 2-(4-methylphenyl)-cyclohexanone prepared using 7-Cl:

[1270] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.17 (d, J=8.0 Hz, 2H), 7.05 (d, J=8.0 Hz, 2H), 3.60 (dd, J=11.9, 5.5 Hz, 1H), 2.41-2.58 (m, 2H), 2.35 (s, 3H), 2.22-2.32 (m, 1H), 2.11-2.21 (m, 1H), 1.93-2.08 (m, 2H), 1.77-1.92 ppm (m, 2H).

[1271] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=210.5, 136.4, 135.7, 129.1, 128.3, 57.0, 42.1, 35.0, 27.8, 25.3, 21.0 ppm.

[1272] MS (EI) m/z (%) 188.1 (100) [M+], 172.1 (10), 144.1 (91), 131.1 (97), 117.1 (51), 105.1 (41), 91.1 (42).

[1273] The NMR data is in agreement with the data in the literature (X.-Q. Hu, D. Lichte, I. Rodstein, P. Weber, A.-K. Seitz, T. Scherpf, V. H. Gessner, L. J. Goo?en, Org. Lett. 2019, 21, 7558-7562).

Further Examples for the ?-Arylation of Ketones

a) 1-(4-methylphenyl)-2-propanone [CAS: 2096-86-8]

[1274] ##STR00149## [1275] Catalyst/Pd source: 1 mol % 7-Cl [1276] Aryl chloride: 64.6 mg of 4-chlorotoluene [1277] Ketone: 58.1 mg of acetone [1278] Yield: 51.0 mg (69%) colorless liquid.

[1279] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.03-7.21 (m, 4H), 3.66 (s, 2H), 2.35 (s, 3H), 2.15 ppm (s, 3H).

[1280] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=206.7, 136.7, 131.2, 129.5, 129.2, 50.7, 29.1, 21.1 ppm.

[1281] MS (EI) m/z (%) 148.0 (28) [M+], 105.0 (100), 91.0 (5), 77.0 (14), 63.0 (3), 51.0 (4).

[1282] The NMR data is in agreement with the data in the literature (X.-Q. Hu, D. Lichte, I. Rodstein, P. Weber, A.-K. Seitz, T. Scherpf, V. H. Gessner, L. J. Goo?en, Org. Lett. 2019, 21, 7558-7562).

b) 2-methyl-1-phenyl-2-(4-methylphenyl)-propanone [CAS: 14271-33-1]

[1283] ##STR00150##

[1284] Catalyst/Pd source: 1 mol % 7-Cl [1285] Aryl chloride: 64.6 mg of 4-chlorotoluene [1286] Ketone: 148 mg of isobutyrophenone [1287] Yield: 110 mg (92%) yellow oil.

[1288] .sup.1H NMR (300 MHz, CDCl.sub.3) ?=7.50-7.53 (m, 1H), 7.47-7.50 (m, 1H), 7.33-7.40 (m, 1H), 7.13-7.26 (m, 6H), 2.35 (s, 3H), 1.59 ppm (s, 6H)

[1289] .sup.13C NMR (75 MHz, CDCl.sub.3) ?=203.9, 142.2, 136.4, 129.7, 127.9, 125.6, 51.0, 27.8, 21.0 ppm

[1290] MS (EI) m/z (%) 238.1 (1) [M+], 207.0 (2), 133.1 (100), 115.1 (7), 105.0 (75), 91.4 (14), 77.0 (24).

[1291] The NMR data is in agreement with the data in the literature (X.-Q. Hu, D. Lichte, I. Rodstein, P. Weber, A.-K. Seitz, T. Scherpf, V. H. Gessner, L. J. Goo?en, Org. Lett. 2019, 21, 7558-7562).

D. General Procedure for the Negishi Coupling

[1292] A solution of the catalyst (0.005 mmol, 0.01 eq.) and 4.76 mg of the ligand RuPhos (0.01 mmol, 0.02 eq.) in 0.5 ml of THE was stirred for 20 min at room temperature in the glove box. The aryl chloride (0.5 mmol, 1 eq.) and 152 ?l of TMEDA (1 mmol, 2 eq.) were added to this solution. Outside the glove box, the arylzinc bromide solution was added to THE (0.75 mmol, 1.5 eq.) using a syringe and the resulting mixture was stirred for 16 h at room temperature. Upon completion, the solution was diluted with 3 ml of EtOAc and washed with 15 ml of water. The aqueous layer was extracted with EtOAc (3?15 ml) and the combined organic layers were washed with saline solution. The combined organic phases were dried over MgSO.sub.4 and the volatile components removed under reduced pressure. The residue was purified by flash column chromatography to obtain the desired biphenyl.

[1293] The preparation of 2-methoxybiphenyl [CAS: 86-26-0] was chosen as model reaction:

##STR00151## [1294] Catalyst/Pd source: 1 mol % 7-Br [1295] Aryl chloride: 72.7 mg of 2-chloroanisole [1296] Arylzinc bromide: 3.00 ml of phenylzinc bromide, solution in THE [1297] * for comparative purposes

TABLE-US-00028 TABLE B-8 Use in Negishi coupling using the example of the preparation of 2- methoxybiphenyl Entry Catalyst Yield [%].sup.a) 1 7-Cl >99 (42) 2 7-Br >99 (36) 3 8-Cl >99 (35) 4 8-Br >99 (7) .sup.a)Value in brackets after 8 h at room temperature.

[1298] With all four palladium-naphthyl catalysts (7-8 Cl/Br) in combination with the phosphine ligand RuPhos, the desired product was formed at a quantitative yield under the reaction conditions given above. In comparison, the use of the Hazari catalyst [Pd(t-bu-indenyl)Cl]2 and of the phosphine ligand RuPhos under otherwise identical reaction conditions led to a 31% yield of the expected compound. Consequently, the four palladium-naphthyl catalysts (7-8 Cl/Br) performed markedly better than the Hazari catalyst.

[1299] Analytical data for 2-methoxybiphenyl prepared using 7-Br and purified by flash column chromatography (SiO2, cyclohexane/EtOAc gradient 0%.fwdarw.10%):

[1300] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.56 (d, J=7.2 Hz, 2H), 7.44 (t, J=8.0 Hz, 2H), 7.30-7.38 (m, 3H), 6.97-7.11 (m, 2H), 3.83 (s, 3H) ppm.

[1301] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=156.6, 138.7, 131.0, 130.8, 129.7, 128.7, 128.1, 127.0, 121.0, 111.3, 55.7 ppm.

[1302] HRMS (ESI) m/z calculated for C.sub.13H.sub.12O [M+H].sup.+ 185.0968, found 185.0961.

[1303] The NMR data is in agreement with the data in the literature (O. Diebolt, V. Jur?ik, R. Correa da Costa, P. Braunstein, L. Cavallo, S. P. Nolan, A. M. Z. Slawin, C. S. J. Cazin, Organometallics 2010, 29, 1443-1450).

Further Examples for Negishi Couplings

a) 2,2-dimethylbiphenyl [CAS: 605-39-0]

[1304] ##STR00152## [1305] Catalyst/Pd source: 1 mol % 7-Br [1306] Aryl chloride: 64.6 mg of 2-chlorotoluene [1307] Arylzinc bromide: 0.18 ml of tolylzinc bromide, solution in THE [1308] Yield: 112 mg (91%) colorless oil, after flash column chromatography (SiO2, pentane).

[1309] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.17-7.21 (m, 4H), 7.11-7.17 (m, 2H), 6.99-7.06 (m, 2H), 1.98 ppm (s, 6H).

[1310] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=141.7, 136.0, 129.9, 129.4, 127.3, 125.7, 20.0 ppm.

[1311] MS (EI) m/z (%) 181.8. (86) [M+], 167.2 (100), 153.0 (4), 139.0 (2), 115.0 (6), 89.1 (5), 63.0 (6).

[1312] The NMR data is in agreement with the data in the literature (D.-H. Lee, M.-J. Jin, Org. Lett. 2011, 13, 252-255).

b) 2-methoxyl-2-methylbiphenyl [CAS: 19853-12-4]

[1313] ##STR00153## [1314] Catalyst/Pd source: 1 mol % 7-Br [1315] Aryl chloride: 72.7 mg of 2-chloroanisole [1316] Arylzinc bromide: 0.18 ml of tolylzinc bromide, solution in THE [1317] Yield: 92 mg (93%) colorless oil, after flash column chromatography (SiO.sub.2, pentane/EtOAc gradient 0% .fwdarw.10%).

[1318] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.40-7.48 (m, 1H), 7.27-7.38 (m, 4H), 7.24 (dd, J=7.4, 1.8 Hz, 1H), 7.12 (dd, J=7.4, 1.1 Hz, 1H), 7.03-7.09 (m, 1H), 3.85 (s, 3H), 2.24 (s, 3H) ppm.

[1319] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=156.7, 138.8, 137.0, 131.1, 131.0, 130.1, 129.7, 128.7, 127.4, 125.6, 120.6, 110.8, 55.5, 20.1 ppm.

[1320] HRMS (ESI) m/z calculated for C.sub.14H.sub.14O [M+H].sup.+ 199.1122, found 199.1123

[1321] The NMR data is in agreement with the data in the literature (S. E. Denmark, R. C. Smith, W.-T. T. Chang, J. M. Muhuhi, J. Am. Chem. Soc. 2009, 131, 3104-3118).

c) 1,3-dimethoxy-2-phenylbenzene [CAS: 13732-86-0]

[1322] ##STR00154## [1323] Catalyst/Pd source: 1 mol % 7-Br [1324] Aryl chloride: 88.1 mg of 2-chloro-1,3-dimethoxybenzene [1325] Arylzinc bromide: 1.5 ml of tolylzinc bromide, solution in THE [1326] Yield: 78 mg (73%), after flash column chromatography (SiO2, pentane/EtOAc gradient 0%.fwdarw.10%) and Kugelrohr distillation.

[1327] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.37-7.44 (m, 2H), 7.32-7.37 (m, 2H), 7.28-7.32 (m, 1H), 7.25 (s, 1H), 6.66 (d, J=8.3 Hz, 2H), 3.73 (s, 6H) ppm.

[1328] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=157.5, 134.0, 130.7, 128.4, 127.5, 126.6, 119.5, 104.1, 55.8 ppm.

[1329] HRMS (ESI) m/z calculated for C.sub.14H.sub.14O.sub.2 [M+H].sup.+ 214.1074, found 214.1074

[1330] The NMR data is in agreement with the data in the literature (T. Truong, O. Daugulis, J. Am. Chem. Soc. 2011, 133, 4243-4245).

d) 2,2,6-trimethylbiphenyl [CAS10273-87-7]

[1331] ##STR00155## [1332] Catalyst/Pd source: 1 mol % 7-Br [1333] Aryl chloride: 71.7 mg of 2-chloro-m-xylene [1334] Arylzinc bromide: 0.18 ml of tolylzinc bromide, solution in THE [1335] Yield: 55 mg (56%) colorless oil, after flash column chromatography (SiO.sub.2, pentane).

[1336] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=7.14-7.24 (m, 3H), 7.06-7.13 (m, 1H), 7.00-7.06 (m, 2H), 6.90-6.97 (m, 1H), 1.89 (s, 3H), 1.87 ppm (s, 6H).

[1337] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=141.2, 140.6, 135.9, 135.6, 130.0, 128.9, 127.2, 127.0, 126.9, 126.1, 20.4, 19.4 ppm.

[1338] MS (EI) m/z (%) 196.2. (63) [M+], 181.1 (2), 178.1 (14), 165.1 (49), 152.1 (9), 115.1 (7), 89.1 (11).

[1339] The NMR data is in agreement with the data in the literature (S. Chun To, F. Yee Kwong, Chem. Commun. 2011, 47, 5079).

e) 5-phenylbenzoxazole [CAS: 201415-38-5]

[1340] ##STR00156## [1341] Catalyst/Pd source: 1 mol % 7-Br [1342] Aryl chloride: 80.8 mg of 5-chlorobenzoxazole [1343] Arylzinc bromide: 1.25 ml of phenylzinc bromide, solution in THE [1344] Yield: 71.0 mg (73%) off-white solid, after flash column chromatography (SiO.sub.2, cyclohexane/EtOAc gradient 0% .fwdarw.20%).

[1345] .sup.1H NMR (400 MHz, CDCl.sub.3) ?=8.13 (s, 1H), 7.99 (br. s, 1H), 7.59-7.66 (m, 4H), 7.43-7.52 (m, 2H), 7.34-7.41 (m, 1H) ppm.

[1346] .sup.13C NMR (101 MHz, CDCl.sub.3) ?=153.2, 149.7, 141.0, 140.8, 138.7, 129.0, 127.7, 127.5, 125.4, 119.2, 111.1 ppm.

[1347] HRMS (ESI) m/z calculated for C.sub.13H.sub.10NO [M+H].sup.+ 196.0762, found 196.0751.

[1348] The NMR data is in agreement with the data in the literature (S. Guo, B. Qian, Y. Xie, C. Xia, H. Huang, Org. Lett. 2011, 13, 522-525).

[1349] The broad applicability of the new compounds according to formula VIII of formula VIII.a claimed here as palladium sources, in particular in coupling reactions, was demonstrated using the example of new dimeric palladium(II)-1-methylnaphthyl halide complexes in Buchwald-Hartwig aminations, Heck vinylations, ?-arylations of ketones and in Negishi and Suzuki-Miyaura couplings. In the case of Buchwald-Hartwig amination and Suzuki-Miyaura coupling, the effect of the new palladium(II) compounds 7-Cl, 7-Br, 8-Cl and 8-Br, which can be prepared starting from 1-methylnaphthyl halides, on the catalyst activity was particularly pronounced. In the case of Suzuki-Miyaura coupling, it was surprisingly possible to extend the reaction to a new class of substrates. In most cases, the bromide complex 7-Br was the most efficient, but in ketone arylation the best results were obtained with the chloride complex 7-Cl.

[1350] The invention is not limited to one of the embodiments described above but may be modified in many ways.

[1351] It is clear that the invention relates to new methods for preparing palladium complexes which make it possible to prepare known products with high purity, in particular with high NMR purity, and in good yields. In addition, novel palladium complexes, which are usually not accessible or are only accessible with great effort using the methods described in the prior art, can be obtained with high purity, in particular with high NMR purity, and in good yields by means of the preparation methods described here. It has surprisingly been found that the compounds that can be prepared by means of the method described here do not contain impurities due to palladium-containing by-products, for example [Pd(dvds)PtBu.sub.3)] and [Pd.sub.2(dvds).sub.3], that are difficult or impossible to separate, in particular due to their solubility behavior, or only contain traces of said impurities (?1000 ppm). The high purity of the end products is particularly advantageous in view of possible uses, for example as precatalysts and/or catalysts. The invention also relates to new palladium complexes that are suitable as precatalysts and/or catalysts, in particular for cross-coupling reactions.

[1352] Any features and advantages resulting from the claims and the description, including constructive details, spatial arrangements, and method steps, may be relevant to the invention, either alone or in the various combinations.