METHOD FOR PREPARING A POLYFLUORINATED COMPOUND

Abstract

A process for preparing a polyfluorinated compound of formula Ar—R.sub.1 (I), wherein Ar—R.sub.1 (I) is an aromatic ring system

##STR00001##

wherein R.sub.1 is selected from the group consisting of SF.sub.4Cl, SF.sub.3, SF.sub.2CF.sub.3, TeF.sub.5, TeF.sub.4CF.sub.3, SeF.sub.3, IF.sub.2, SeF.sub.2CF.sub.3, and IF.sub.4, X.sub.2 is N or CR.sub.2, X.sub.3 is N or CR.sub.3, X.sub.4 is N or CR.sub.4, X.sub.5 is N or CR.sub.5, X.sub.6 is N or CR.sub.6, and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3, wherein R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, methylcarbonyl, ethylcarbonyl, acetoxy, t-butyl, phenylcarbonyl, benzylcarbonyl, 3-trifluoromethylphenyl, phenylsulfonyl, methylsulfonyl, chlorophenyl, methyldoxolonyl, methyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluoromethyl, fluoroethyl and phenyl.

Claims

1. A process for preparing a polyfluorinated compound of formula
Ar—R.sub.1  (I), wherein Ar—R.sub.1 (I) is an aromatic ring system ##STR00144## wherein R.sub.1 is selected from the group consisting of SF.sub.4Cl, SF.sub.3, SF.sub.2CF.sub.3, TeF.sub.5, TeF.sub.4CF.sub.3, SeF.sub.3, IF.sub.2, SeF.sub.2CF.sub.3 and IF.sub.4, X.sub.2 is N or CR.sub.2, X.sub.3 is N or CR.sub.3, X.sub.4 is N or CR.sub.4, X.sub.5 is N or CR.sub.5, X.sub.6 is N or CR.sub.6, and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3, wherein R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, methylcarbonyl, ethylcarbonyl, acetoxy, t-butyl, phenylcarbonyl, benzylcarbonyl, 3-trifluoromethylphenyl, phenylsulfonyl, methylsulfonyl, chlorophenyl, methyldoxolonyl, methyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluoromethyl, fluoroethyl and phenyl, or if X.sub.5 is CR.sub.5 and X.sub.6 is CR.sub.6R.sub.5 and R.sub.6 may form together a saturated or unsaturated five or six membered ring system comprising one or more nitrogen, wherein the five or six membered ring system may be substituted with one or more residues R.sub.7 having the same definition as R.sub.2 to R.sub.6, and with the proviso that if R.sub.1 is SF.sub.3, at least one of R.sub.2 and R.sub.6 is neither hydrogen nor fluoro and if R.sub.1 is not SF.sub.3, R.sub.2 and R.sub.6 are independently from each other either hydrogen or fluoro and if at least one of X.sub.2, X.sub.3, X.sub.4, X.sub.5 and X.sub.6 is nitrogen, at least one of R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 is not hydrogen the process involving the following reaction step reacting a starting material selected from the group consisting of Ar.sub.2S.sub.2, Ar.sub.2Te.sub.2, Ar.sub.2Se.sub.2, ArSCF.sub.3, ArTeCF.sub.3, ArI, ArSeCF.sub.3, ArSCH.sub.3, and ArSCl, wherein Ar has the same definition as above, with trichloroisocyanuric acid (TCICA) of the formula ##STR00145## in the presence of an alkali metal fluoride (MF).

2. The process for preparing a polyfluorinated compound according to claim 1 wherein Ar—R.sub.1 (I) is an aromatic ring system ##STR00146## wherein R.sub.1 is selected from the group consisting of SF.sub.4Cl, SF.sub.3, SF.sub.2CF.sub.3, TeF.sub.5, TeF.sub.4CF.sub.3, SeF.sub.3, and IF.sub.2, X.sub.2 is N or CR.sub.2, X.sub.3 is N or CR.sub.3, X.sub.4 is N or CR.sub.4, X.sub.5 is N or CR.sub.5, X.sub.6 is N or CR.sub.6, and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3, wherein R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, acetoxy, t-butyl and phenyl, and with the proviso that if R.sub.1 is SF.sub.3, at least one of R.sub.2 and R.sub.6 is neither hydrogen nor fluoro and if R.sub.1 is not SF.sub.3, R.sub.2 and R.sub.6 are independently from each other either hydrogen or fluoro and if at least one of X.sub.2, X.sub.3, X.sub.4, X.sub.5 and X.sub.6 is nitrogen, at least one of R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 is not hydrogen the process involving the following reaction step reacting a starting material selected from the group consisting of Ar.sub.2S.sub.2, Ar.sub.2Te.sub.2, Ar.sub.2Se.sub.2, Ar—SCF.sub.3 and ArI, wherein Ar has the same definition as above, with trichloroisocyanuric acid (TCICA) of the formula ##STR00147## in the presence of an alkali metal fluoride (MF).

3. The process according to claim 1, wherein the process is carried out in the presence of a catalytic amount of a Brønsted or Lewis acid.

4. The process according to claim 3, wherein the catalytic amount of the Brønsted or Lewis acid is between 5 mol % and 15 mol %.

5. The process according to claim 1, wherein the molar ratio of TCICA:MF is between 1:1 and 1:10.

6. The process according to claim 1 for preparing a polyfluorinated compound of formula Ar—R.sub.1 (I).

7. The process according to claim 1, wherein R.sub.1 is SF.sub.4Cl or SF.sub.3.

8. The process according to claim 1, wherein the aromatic ring system is a substituted or unsubstituted phenyl ring and R.sub.1 to R.sub.6 have the same definition as in claim 1.

9. The process according to claim 1, wherein at least one of X.sub.2, X.sub.3, X.sub.4, X.sub.5 and X.sub.6 is nitrogen.

10. The process according to claim 8, wherein exactly two of X.sub.2, X.sub.3, X.sub.4, X.sub.5 and X.sub.6 are nitrogen.

11. The process according to claim 1, wherein at least one of R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 is fluoro, chloro, bromo, methoxycarbonyl, ethoxycarbonyl or acetoxy.

12. The process according to claim 1, wherein the starting material is a diaryl dichalcogenide or a diheteroaryl dichalcogenide selected from the group consisting of Ar.sub.2S.sub.2, Ar.sub.2Te.sub.2 and Ar.sub.2Se.sub.2.

13. The process according to claim 1, wherein the starting material is Ar—SCF.sub.3 or ArI.

14. The process according to claim 1 by reacting Ar—SF.sub.4Cl in a second reaction step to obtain a compound of formula (V) or (VI) ##STR00148## wherein X.sub.2 is N or CR.sub.2, X.sub.3 is N or CR.sub.3, X.sub.4 is N or CR.sub.4, X.sub.5 is N or CR.sub.5, X.sub.6 is N or CR.sub.6, and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3, R.sub.2 and R.sub.6 are independently from each other either hydrogen or fluoro and R.sub.3, R.sub.4, and R.sub.5 are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, acetoxy, t-butyl and phenyl, and R.sub.10 is linear or branched, substituted or unsubstituted alkyl, α-alkenyl or α-alkynyl having 2 to 10 carbon atoms.

15. A compound of formula ##STR00149## selected from the group consisting of TABLE-US-00003 Compound No. R.sub.1 X.sub.2 X.sub.3 X.sub.4 X.sub.5 X.sub.6 101 SF.sub.4Cl C—H C—H C—NO.sub.2 C—COOMe C—H 102 SF.sub.4Cl C—H C—H C—H C—COOEt C—H 103 SF.sub.4Cl C—H C—H C—OAc C—H C—H 104 SF.sub.4Cl C—H C—H C—NPhth C—H C—H 105 SF.sub.4Cl C—H C—H C—OCF.sub.3 C—H C—H 106 SF.sub.4Cl C—H C—H C—SF.sub.5 C—H C—H 107 SF.sub.4Cl N C—H C—COOMe C—H C—H 108 SF.sub.4Cl N N C—Ph C—Ph N 109 SF.sub.5 C—H C—H C—NO.sub.2 C—COOMe C—H 111 SF.sub.5 C—H C—H C—OAc C—H C—H 112 SF.sub.5 C—H C—H C—NO.sub.2 C—COOH C—H 116 SF.sub.5 C—H C—H C—OCF.sub.3 C—H C—H 118 SF.sub.5 N C—H C—COOMe C—H C—H 119 SF.sub.5 N N C—Ph C—Ph N 120 SF.sub.5 N C—H C—COOH C—H C—H 121 SF.sub.4Cl C—H O—Bz C—H C—H C—H 122 SF.sub.4Cl C—H C—H O—Bz C—H C—H 123 SF.sub.4Cl C—F O—Bz C—H C—H C—H 124 SF.sub.4Cl C—F C—H O—Bz C—H C—H 125 SF.sub.4Cl C—F C—H C—H O—Bz C—H 126 SF.sub.5 C—H O—Bz C—H C—H C—H 127 SF.sub.5 C—F O—Bz C—H C—H C—H 128 SF.sub.5 C—F C—H C—H O—Bz C—H 129 SF.sub.4Cl C—H C—N.sub.3 C—H C—H C—H 130 SF.sub.4Cl C—H C—H C—N.sub.3 C—H C—H 131 SF.sub.4Cl C—F C—N.sub.3 C—H C—H C—H 132 SF.sub.4Cl C—F C—H C—N.sub.3 C—H C—H 133 SF.sub.4Cl C—F C—H C—H C—N.sub.3 C—H

Description

EXPERIMENTS

Example 1: General Procedure for Synthesis of Aryl Tetrafluoro-λ.SUP.6.-Sulfanyl Chloride Compounds

[0102] ##STR00027##

[0103] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the disulfide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h).

[0104] Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0105] In order to remove KF and TCICA (and its byproducts) outside of the glove box, the crude reaction mixture was first filtered into a polyethylene centrifuge tube and concentrated by blowing N.sub.2 over it. Then, it was diluted with dry pentane, filtered into a polyethylene centrifuge tube, and concentrated by blowing N.sub.2 over it. The crude material consisted of mostly the aryl-SF.sub.4Cl product (amount quantified by .sup.19F NMR) and was carried forward without further purification.

[0106] Alternatively, for more moisture sensitive products, the reaction vessel atmosphere was purged with Ar and transported into the glovebox. Subsequently, the crude reaction mixture was filtered into a PFA vessel via syringe filter and concentrated in vacuo. Then, it was diluted with dry hexanes, filtered into a PFA vessel, and concentrated in vacuo. The crude material consisted of mostly the aryl-SF.sub.4Cl product (amount quantified by .sup.19F NMR) and was carried forward without further purification.

[0107] Representative Product

##STR00028##

[0108] 70% yield (by .sup.19F NMR). The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): +136.61 (4F, s).

Example 2: General Procedure for Synthesis of Aryl Sulfur Trifluoride Compounds

[0109] ##STR00029##

[0110] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the disulfide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Note that substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0111] Representative Product

##STR00030##

[0112] 92% yield (by .sup.19F NMR). The reaction was run according to the general procedure. .sup.19F NMR (471 MHz, CD.sub.3CN): +63.46 (2F, d, J=75.6 Hz), −56.31 (1F, t, J=75.6 Hz).

Example 3: General Procedure for Synthesis of Aryl Selenium Trifluoride Compounds

[0113] ##STR00031##

[0114] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the diselenide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0115] Representative Product

##STR00032##

[0116] 95% yield (by .sup.19F NMR). The reaction was run according to the general procedure. The product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): −25.51 (3F, br s).

Example 4: General Procedure for Synthesis of Aryl Pentafluorotelluryl Compounds

[0117] ##STR00033##

[0118] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the ditelluride substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0119] Representative Product

##STR00034##

[0120] >90% yield (by .sup.19F NMR). The reaction was run according to the general procedure. The product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): −37.60 (1F, quint, J=148.6 Hz), −54.50 (4F, quint, J=148.6 Hz).

Example 5: General Procedure for Synthesis of Difluoro(Aryl)(Trifluoromethyl)-λ.SUP.4.-Sulfane Compounds

[0121] ##STR00035##

[0122] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl(trifluoromethyl)sulfane substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0123] Representative Product

##STR00036##

[0124] 81% yield (by .sup.19F NMR). The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −14.38 (2F, q, J=18.0 Hz), −62.79 (3F, t, J=18.0 Hz).

Example 6: General Procedure for Synthesis of Tetrafluoro(Aryl)(Trifluoromethyl)-λ.SUP.6.-Tellane Compounds

[0125] ##STR00037##

[0126] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl(trifluoromethyl)tellane substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0127] Representative Product

##STR00038##

[0128] >95% yield (by .sup.19F NMR). The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −54.10 (3F, quint, J=22.5 Hz), −68.73 (4F, q, J=22.5 Hz).

Example 8: General Procedure for Synthesis of Aryl Difluoroiodane Compounds

[0129] ##STR00039##

[0130] Trichloroisocyanuric acid (0.32 g, 1.4 mmol, 6.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.07 g, 1.2 mmol, 5.0 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl iodide substrate (0.23 mmol, 1.0 equiv.) in 2.0 mL MeCN was added to the vial, and the reaction mixture was stirred at 40° C. for ca. 24 h. Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0131] Representative Product

##STR00040##

[0132] 97% yield (by .sup.19F NMR). The reaction was run according to the general procedure. The product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): −97.44 (2F, t, J=2.3 Hz), −165.67 (2F, t, J=2.3 Hz).

Example 9: Procedure for Synthesis of SFSCl

[0133] ##STR00041##

[0134] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, followed by elemental sulfur (0.46 mmol, 1.0 equiv.). The reaction vessel was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Upon reaction completion, the head space of the vial was drawn up into a syringe for GC/MS analysis. Subsequently, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR analysis.

[0135] The product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): 124.26 (4F, d, J=151.2 Hz), 64.15 (1F, d, J=151.2 Hz).

Example 10: General Procedure for Synthesis of

[0136] Pentafluorosulfanyl Compounds

##STR00042##

[0137] A solution of a known amount of aryl-SF.sub.4Cl compound (1.0 equiv.) in anhydrous CH.sub.2Cl.sub.2 was transferred to a copper (or PFA) vessel and concentrated. Subsequently, AgF (2.0 equiv.) was added, and the reactor was sealed under Ar atmosphere. The sealed reactor was heated to 120° C. for ca. 2 days. Upon cooling, the reactor was rinsed with copious amounts of CH.sub.2Cl.sub.2 and H.sub.2O into a separatory funnel. The reaction mixture was extracted with CH.sub.2Cl.sub.2. The combined organic layers were dried with MgSO.sub.4, filtered through Celite, and concentrated. The crude reaction mixture was purified via gradient column chromatography on a Teledyne-Isco Combiflash instrument, eluting with hexanes:EtOAc.

[0138] Representative Product

##STR00043##

[0139] 77% yield (isolated). The reaction was run according to the general procedure using AgF in a copper vessel; the product was isolated via gradient column chromatography on silica gel in as a white solid. .sup.19F NMR (377 MHz, CDCl.sub.3): 84.32 (1F, quint, J=150.6 Hz), 63.62 (4F, d, J=150.6 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.78 (2H, dm, J=9.1 Hz), 7.20 (2H, d, J=9.1 Hz), 2.33 (3H, s); .sup.13C {.sup.1H} NMR (101 MHz, CDCl.sub.3): 168.7, 152.5, 150.9 (quint, J=18.0 Hz), 127.5 (quint, J=4.8 Hz), 121.8, 21.0.

Example 11: General Procedure for Synthesis of Aryl Tetrafluoro-λ.SUP.6.-sulfanyl Chloride Alkanes/Alkenes

[0140] ##STR00044##

[0141] A solution of a known amount of aryl-SF.sub.4Cl compound (1.0 equiv.) in anhydrous CH.sub.2Cl.sub.2 (0.05-0.1 M) was transferred to a PFA vessel equipped with a stir bar under Ar atmosphere. The alkene or alkyne substrate (1.5 equiv.) was added, followed by 10 mol % BEt.sub.3 (administered as a 1.0 M solution in hexanes), and the reaction mixture was stirred at room temperature for 1 h. At this time, the reaction mixture was quenched with saturated aq. NaHCO.sub.3 and extracted into CH.sub.2Cl.sub.2. The combined organic layers were dried with MgSO.sub.4, filtered through Celite, and concentrated. The crude reaction mixture was purified via gradient column chromatography on a Teledyne-Isco Combiflash instrument, eluting with hexanes:EtOAc.

[0142] Representative Products

##STR00045##

[0143] 84% yield (isolated). The reaction was run according to the general procedure using 4-phenyl-1-butene and BEt.sub.3; the product was isolated via gradient column chromatography on silica gel as a white solid. .sup.19F NMR (377 MHz, CDCl.sub.3): 57.59 (4F, t, J=8.5 Hz, becomes s in .sup.19F{.sup.1H} spectrum); .sup.1H NMR (400 MHz, CDCl.sub.3): 9.10 (1H, d, J=2.1 Hz), 8.44 (1H, d, J=8.5 Hz), 7.80 (1H, d, J=8.5 Hz), 7.34-7.21 (5H, m), 4.60-4.54 (1H, m), 4.46-4.34 (1H, m, becomes dd, J=13.7, 5.3 Hz in .sup.1H{.sup.19F} spectrum), 4.33-4.20 (1H, m, becomes dd, J=13.7, 7.2 Hz in .sup.1H{.sup.19F} spectrum), 4.00 (3H, s), 3.00 (1H, ddd, J=14.0, 9.2, 4.5 Hz), 2.87-2.80 (1H, m), 2.52-2.44 (1H, m), 2.18-2.08 (1H, m); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 172.6 (quint, J=31.7 Hz), 164.3, 148.6 (m), 140.2, 139.6, 128.53, 128.49, 127.9, 126.3, 121.1 (quint, J=4.8 Hz), 81.6 (quint, J=18.7 Hz), 56.5 (quint, J=5.2 Hz), 52.8, 39.2, 32.3.

##STR00046##

[0144] 70% yield (isolated). The reaction was run according to the general procedure using phenylacetylene and BEt.sub.3; the product was isolated via gradient column chromatography on silica gel as a white solid. .sup.19F NMR (282 MHz, CD.sub.3CN): 71.26 (4F, d, J=8.4 Hz, becomes s in .sup.19F{.sup.1H} spectrum); .sup.1H NMR (400 MHz, CDCl.sub.3): 8.01 (1H, dm, J=2.2 Hz), 7.86 (1H, dd, J=8.9, 2.2 Hz), 7.81 (1H, dm, J=8.9 Hz), 7.43-7.38 (5H, m), 7.18 (1H, quint, J=8.4 Hz), 3.91 (3H, s); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 164.2, 161.7 (quint, J=27.6 Hz), 148.6, 143.0 (quint, J=28.6 Hz), 139.8 (quint, J=7.8 Hz), 136.5, 129.7 (quint, J=5.4 Hz), 129.5, 128.1, 127.9 (m), 127.2, 123.8, 53.6.

Example 12: Representative Procedure for Synthesis of Difluoro(aryl)(trifluoromethyl)-λ.SUP.4.-sulfane Compound and Application as Putative Nucleophilic Fluorinating Reagent

[0145] ##STR00047##

[0146] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N.sub.2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl(trifluoromethyl)sulfane substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD.sub.3CN) for .sup.19F NMR yield determination.

[0147] In order to remove KF and TCICA (and its byproducts) outside of the glove box, the crude reaction mixture was first filtered into a polyethylene centrifuge tube and concentrated by blowing N.sub.2 over it. Then, it was diluted with dry pentane, filtered into a polyethylene centrifuge tube, and concentrated by blowing N.sub.2 over it. The crude material consisted of mostly the aryl-SF.sub.4Cl product (amount quantified by .sup.19F NMR) and was carried forward without further purification (˜0.34 mmol isolated aryl-SF.sub.2CF.sub.3 based on .sup.19F NMR analysis).

[0148] A solution of the difluoro(aryl)(trifluoromethyl)-λ.sup.4-sulfane substrate (˜0.34 mmol, 1.0 equiv.) in 4 mL CHCl.sub.3 was added to an oven-dried microwave vial equipped with a stir bar and sealed with a cap with septum under Ar atmosphere. Subsequently, 4-fluorobenzyl alcohol (0.04 mL, 0.37 mmol, 1.1 equiv.) was added to the vial, and the reaction mixture was stirred at room temperature. After 45 min, an aliquot was taken from the reaction mixture for .sup.19F NMR analysis. (Note: trifluorotoluene was added to the solution as an internal reference, but not for quantification purposes.) Representative Products

##STR00048##

[0149] 77% yield (by .sup.19F NMR). The reaction was run according to the representative procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.99 (2F, q, J=17.9 Hz), −62.77 (3F, t, J=17.9 Hz).

##STR00049##

[0150] The reaction was run according to the representative procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −113.51 (1F, m), −203.83 (1F, t, J=48.1 Hz).

Example 13: General Procedure for Synthesis of Trifluoromethyl Tetrafluoro-λ6-Sulfanyl Chloride

[0151] ##STR00050##

[0152] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the disulfide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared for 19F NMR analysis.

[0153] The product (synthesized from 1-(4-nitrophenyl)-2-(trifluoromethyl)disulfide) is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN): trans-isomer: +102.88 (4F, q, J=22.2 Hz), −65.39 (3F, quint, J=22.2 Hz); cis-isomer: +134.48 (1F, qq, J=146.6, 9.1 Hz), +83.55 (2F, ddq, J=146.6, 102.9, 19.7 Hz), +40.83 (1F, dtq, J=146.6, 102.9, 22.8 Hz), −65.95 (3F, dtd, J=22.8, 19.7, 9.1 Hz). cis:trans ratio: 3:1.

Example 14: General Procedure for Synthesis of Diaryl Tetrafluoro-λ6-tellane Compounds

[0154] ##STR00051##

[0155] Trichloroisocyanuric acid (0.319 g, 1.4 mmol, 3.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.319 g, 5.5 mmol, 12 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the diaryl monotelluride substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 20 h). Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

[0156] Representative Product

##STR00052##

[0157] 39% trans and 6% cis observed by 19F NMR. The products are consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN): trans-isomer: −58.11 (4F, s); cis-isomer: −37.07 (2F, t, J=87.5 Hz), −77.29 (2F, t, J=87.5 Hz).

Example 15: General Procedure for Synthesis of Aryl Tetrafluoro-λ6-Sulfanyl Chloride Compounds

[0158] ##STR00053##

[0159] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 18 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the sulfenyl chloride substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

[0160] Representative Product

##STR00054##

[0161] 68% yield by 19F NMR. The product (synthesized from 4-nitrobenzenesulfenyl chloride) is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN): +135.02 (4F, s).

Example 16: General Procedure for Synthesis of Aryl Tetrafluoro-λ6-Sulfanyl Chloride Compounds

[0162] ##STR00055##

[0163] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 18 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl methyl sulfide substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

[0164] Representative Product

##STR00056##

[0165] The product is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN): +136.61 (4F, s).

Example 17: General Procedure for Synthesis of Difluoro(Aryl)(Trifluoromethyl)-λ4-Selane Compounds

[0166] ##STR00057##

[0167] Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl(trifluoromethyl)selane substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

[0168] Representative Product

##STR00058##

[0169] 71% yield (by 19F NMR). The reaction was run according to the general procedure. 19F NMR (282 MHz, CD3CN): −58.30 (3F, t, J=12.2 Hz), −73.21 (4F, t, J=12.2 Hz).

Example 18: General Procedure for Synthesis of Tetrafluoro(Aryl)-λ5-Iodane Compounds

[0170] ##STR00059##

[0171] Trichloroisocyanuric acid (0.350 g, 1.5 mmol, 4.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.131 g, 2.3 mmol, 6.0 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl iodide substrate (0.38 mmol, 1.0 equiv.) in 4.0 mL MeCN was added to the vial. The reaction mixture was stirred vigorously at room temperature for ca. 48 h. Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring). Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot+0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

[0172] Representative Product

##STR00060##

[0173] 85% yield by 19F NMR. The product is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN): −25.86 (4F, br s), −104.29 to −104.46 (1F, m).

[0174] The following compounds were synthesized using the reaction conditions described above:

##STR00061##

[0175] The reaction was run according to the general procedure, and the product was converted to the more stable aryl tetrafluoro-λ.sup.6-sulfanyl alkene 232 to obtain complete characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +134.63 (4F, s).

##STR00062##

[0176] The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene 227 to obtain complete characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +135.95 (4F, s)

##STR00063##

[0177] The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene 111 to obtain complete characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +137.43 (4F, s).

##STR00064##

[0178] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): +136.81 (4F, s) Compound 105.

##STR00065##

[0179] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): +136.73 (4F, s), −58.56 (3F, s)

##STR00066##

[0180] The reaction was run according to the general procedure. .sup.19F NMR (377 MHz, CD.sub.3CN): +134.96 (4F, s), +81.54 (1F, quint, J=148.5 Hz), +61.86 (4F, d, J=148.5 Hz).

##STR00067##

[0181] The reaction was run according to the general procedure, and the product was converted to the more stable aryl tetrafluoro-λ.sup.6-sulfanyl alkane 228 to obtain complete characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +123.52 (4F, s).

##STR00068##

[0182] The reaction was run according to the general procedure. .sup.19F NMR (377 MHz, CD.sub.3CN): +120.59 (4F, s)

##STR00069##

[0183] The reaction was run according to the general procedure using AgF in a copper vessel; the product was isolated via gradient column chromatography on silica gel in 77% yield (46 mg, 0.18 mmol) as a white solid. .sup.19F NMR (377 MHz, CDCl.sub.3): 84.32 (1F, quint, J=150.6 Hz), 63.62 (4F, d, J=150.6 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.78 (2H, dm, J=9.1 Hz), 7.20 (2H, d, J=9.1 Hz), 2.33 (3H, s); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 168.7, 152.5, 150.9 (quint, J=18.0 Hz), 127.5 (quint, J=4.8 Hz), 121.8, 21.0.

##STR00070##

[0184] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): +136.61 (4F, s).

##STR00071##

[0185] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +136.08 (4F, s), −111.34 (1F, m).

##STR00072##

[0186] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): +137.65 (4F, s), −108.21 (1F, m).

##STR00073##

[0187] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +136.75 (4F, s).

##STR00074##

[0188] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +136.59 (4F, s).

##STR00075##

[0189] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): +135.61 (4F, s), −63.21 (3F, s)

##STR00076##

[0190] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): +135.02 (4F, s)

##STR00077##

[0191] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +140.30 (4F, d, J=24.5 Hz), −110.04 (1F, m)

##STR00078##

[0192] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +137.64 (4F, s)

##STR00079##

[0193] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +124.66 (4F, s).

##STR00080##

[0194] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): +123.42 (4F, s)

##STR00081##

[0195] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +119.06 (4F, s).

##STR00082##

[0196] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +118.97 (4F, s).

##STR00083##

[0197] The reaction was run according to the general procedure; the product was unstable toward isolation and characterized by .sup.19F NMR. .sup.19F NMR (471 MHz, CD.sub.3CN): +63.46 (2F, d, J=75.6 Hz), −56.31 (1F, t, J=75.6 Hz).

##STR00084##

[0198] The reaction was run according to the general procedure; the product was unstable toward isolation and characterized by .sup.19F NMR. .sup.19F NMR (377 MHz, CD.sub.3CN)+53.58 (2F, d, J=102.2 Hz), −67.65 (1F, t, J=102.2 Hz).

##STR00085##

[0199] The reaction was run according to the general procedure; the product was unstable toward isolation and characterized by .sup.19F NMR. The product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CD.sub.3CN): −25.51 (3F, br s).

##STR00086##

[0200] The reaction was run according to the general procedure using AgF in a copper vessel followed by the LiOH workup modification; the product was isolated via gradient column chromatography on silica gel in 68% yield (21 mg, 0.10 mmol) as a white solid. The product is consistent with previously reported characterization data. .sup.19F NMR (377 MHz, CDCl.sub.3): 86.05 (1F, quint, J=150.0 Hz), 64.32 (4F, d, J=150.0 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.65 (2H, dm, J=9.1 Hz), 6.86 (2H, dm, J=9.1 Hz), 5.17 (1H, br s).

##STR00087##

[0201] The reaction was run according to the general procedure using AgF in a copper vessel; the product was isolated via gradient column chromatography on silica gel in 57% yield (20 mg, 0.07 mmol) as a colorless oil. .sup.19F NMR (471 MHz, CDCl.sub.3): 83.35 (1F, quint, J=150.4 Hz), 62.79 (4F, d, J=150.4 Hz); .sup.1H NMR (500 MHz, CDCl.sub.3): 8.43 (1H, m), 8.20 (1H, d, J=7.8 Hz), 7.94 (1H, m), 7.56 (1H, t, J=8.0 Hz), 4.43 (2H, q, J=7.1 Hz), 1.42 (3H, t, J=7.1 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CDCl.sub.3): 164.8, 153.9 (quint, J=18.2 Hz), 132.5, 131.5, 130.0 (quint, J=4.6 Hz), 128.9, 127.2 (quint, J=4.6 Hz), 61.8, 14.3.

##STR00088##

[0202] The reaction was run according to the general procedure using 4-phenyl-1-butene and BEt.sub.3; the product was isolated via gradient column chromatography on silica gel in 84% yield (25 mg, 0.06 mmol) as a white solid. Although this product proved stable toward column chromatography, note that it degraded after a few days in CDCl.sub.3 solution in the NMR tube. .sup.19F NMR (377 MHz, CDCl.sub.3): 57.59 (4F, t, J=8.5 Hz, becomes s in .sup.19F{.sup.1H} spectrum); .sup.1H NMR (400 MHz, CDCl.sub.3): 9.10 (1H, d, J=2.1 Hz), 8.44 (1H, d, J=8.5 Hz), 7.80 (1H, d, J=8.5 Hz), 7.34-7.21 (5H, m), 4.60-4.54 (1H, m), 4.46-4.34 (1H, m, becomes dd, J=13.7, 5.3 Hz in .sup.1H{.sup.19F} spectrum), 4.33-4.20 (1H, m, becomes dd, J=13.7, 7.2 Hz in .sup.1H{.sup.19F} spectrum), 4.00 (3H, s), 3.00 (1H, ddd, J=14.0, 9.2, 4.5 Hz), 2.87-2.80 (1H, m), 2.52-2.44 (1H, m), 2.18-2.08 (1H, m); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 172.6 (quint, J=31.7 Hz), 164.3, 148.6 (m), 140.2, 139.6, 128.53, 128.49, 127.9, 126.3, 121.1 (quint, J=4.8 Hz), 81.6 (quint, J=18.7 Hz), 56.5 (quint, J=5.2 Hz), 52.8, 39.2, 32.3.

##STR00089##

[0203] The reaction was run according to the general procedure using phenylacetylene and BEt.sub.3; the product was isolated via gradient column chromatography on silica gel in 70% yield (40 mg, 0.09 mmol) as a white solid. Although this product proved stable toward column chromatography, note that it degraded after a few days in CDCl.sub.3 solution in the NMR tube. .sup.19F NMR (282 MHz, CD.sub.3CN): 71.26 (4F, d, J=8.4 Hz, becomes s in .sup.19F{.sup.1H} spectrum); .sup.1H NMR (400 MHz, CDCl.sub.3): 8.01 (1H, dm, J=2.2 Hz), 7.86 (1H, dd, J=8.9, 2.2 Hz), 7.81 (1H, dm, J=8.9 Hz), 7.43-7.38 (5H, m), 7.18 (1H, quint, J=8.4 Hz), 3.91 (3H, s); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 164.2, 161.7 (quint, J=27.6 Hz), 148.6, 143.0 (quint, J=28.6 Hz), 139.8 (quint, J=7.8 Hz), 136.5, 129.7 (quint, J=5.4 Hz), 129.5, 128.1, 127.9 (m), 127.2, 123.8, 53.6.

##STR00090##

[0204] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): trans-isomer: +143.21 (4F, t, J=27.6 Hz), −135.35 (2F, m), −148.85 (1F, m), −161.05 (2F, m); cis-isomer: +153.07 (1F, q, J=158.3 Hz), +122.77 (2F, ddd, J=158.3, 95.1, 78.2 Hz), +79.21 (1F, dtt, J=158.3, 95.1, 20.9 Hz), −135.35 (2F, m), −148.85 (1F, m), −161.05 (2F, m) trans:cis ratio: 1.5:1.

##STR00091##

[0205] The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene to obtain complete characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +136.39 (4F, s)

##STR00092##

[0206] The reaction was run according to the general procedure using 4.0 equiv. AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 81% yield (23 mg, 0.07 mmol) as a yellow oil. .sup.19F NMR (471 MHz, CDCl.sub.3): 83.53 (1F, quint, J=150.8 Hz), 63.08 (4F, d, J=150.8 Hz); .sup.1H NMR (500 MHz, CDCl.sub.3): 8.22-8.20 (2H, m), 7.70-7.66 (3H, m), 7.56-7.53 (3H, m), 7.44-7.43 (1H, m); .sup.13C{.sup.1H} NMR (126 MHz, CDCl.sub.3): 164.6, 154.3 (quint, J=18.2 Hz), 150.5, 134.1, 130.3, 129.5, 128.7, 125.3, 123.4 (quint, J=4.6 Hz), 120.1 (quint, J=4.6 Hz). □.sub.max (ATR-IR): 1743 cm.sup.−1. HRMS (ESI-TOF): calc'd for C.sub.13H.sub.9F.sub.5NaO.sub.2S [M+Na].sup.+: 347.0136, found: 347.0131.

##STR00093##

[0207] The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene to obtain complete characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +135.78.

##STR00094##

[0208] The reaction was run according to the general procedure using AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 57% yield (18 mg, 0.06 mmol) as a white solid; m.p. 116.4-117.3° C. .sup.19F NMR (377 MHz, CDCl.sub.3): 83.11 (1F, quint, J=150.4 Hz), 62.64 (4F, d, J=150.4 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.90-7.85 (4H, m), 7.82-7.79 (2H, m), 7.66-7.62 (1H, tm, J=7.4 Hz), 7.54-7.49 (2H, m); .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3): 194.9, 156.2 (quint, J=18.1 Hz), 140.3, 136.5, 133.3, 130.09, 130.08, 128.6, 126.1 (quint, J=4.7 Hz). □.sub.max (ATR-IR): 1653 cm.sup.−1. HRMS (EI) calculated for Cl.sub.3H.sub.9F.sub.5OS [M].sup.+: 308.0289, found: 308.0282.

##STR00095##

[0209] The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene to obtain complete characterization data. .sup.19F NMR (282 MHz, CD.sub.3CN): +137.77 (4F, s).

##STR00096##

[0210] The reaction was run according to the general procedure using AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 63% yield (21.3 mg, 0.09 mmol) as a light yellow oil. .sup.19F NMR (471 MHz, CDCl.sub.3): 84.59 (1F, quint, J=150.8 Hz), 63.67 (4F, quint, J=150.8 Hz); .sup.1H NMR (500 MHz, CDCl.sub.3): 7.74 (2H, d, J=9.0 Hz), 7.08 (2H, d, J=9.0 Hz). The product is consistent with previously reported characterization data.

##STR00097##

[0211] The reaction was run according to the general procedure using 4.0 equiv. AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 80% yield (6.9 mg, 0.02 mmol) as a white solid; m.p. 217.2-219.0° C. .sup.19F NMR (471 MHz, CDCl.sub.3): 83.79 (1F, quint, J=150.5 Hz), 63.14 (4F, d, J=150.5 Hz); .sup.1H NMR (500 MHz, CDCl.sub.3): 7.99 (2H, dd, J=5.4, 3.1 Hz), 7.90 (2H, d, J=9.1 Hz), 7.84 (2H, dd, J=5.4, 3.1 Hz), 7.65 (2H, d, J=9.1 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CDCl.sub.3): 166.6, 152.5 (quint, J=18.2 Hz), 134.8, 134.6, 131.4, 126.9 (quint, J=4.5 Hz), 126.1, 124.1. □.sub.max (ATR-IR): 1720, 1711, 1702 cm.sup.−1. HRMS (ESI-TOF): calc'd for C.sub.14H.sub.9F.sub.5NO.sub.2S [M+H].sup.+: 350.0269, found: 350.0268. The product is consistent with previously reported characterization data.

##STR00098##

[0212] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): +137.59 (4F, s).

##STR00099##

[0213] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): +137.13 (4F, s)

##STR00100##

[0214] The reaction was run according to the general procedure using AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 59% yield (20 mg, 0.06 mmol) as a white solid; m.p. 82.8-84.8° C. .sup.19F NMR (471 MHz, CDCl.sub.3): +84.60 (1F, quint, J=150.2 Hz), +63.24 (4F, d, J=150.2 Hz); .sup.1H NMR (500 MHz, CDCl.sub.3): 7.83 (2H, dm, J=8.6 Hz), 7.62 (2H, br d, J=8.6 Hz), 7.52 (2H, dm, J=8.6 Hz), 7.45 (2H, dm, J=8.6 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CDCl.sub.3): 153.1 (quint, J=17.5 Hz), 143.3, 137.5, 134.8, 129.3, 128.5, 127.1, 126.6 (quint, J=4.6 Hz). □.sub.max (ATR-IR): 840 cm.sup.−1 (br), 813 cm.sup.−1.

##STR00101##

[0215] The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. Colorless oil. .sup.19F NMR (282 MHz, CDCl.sub.3): −37.11 (1F, quint, J=150.6 Hz), −53.39 (4F, d, J=150.6 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.92 (2H, d, J=8.1 Hz), 7.83-7.78 (1H, m), 7.75-7.70 (2H, m); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 142.2-141.9 (m), 135.4, 131.4 (quint, J=1.5 Hz), 130.3 (quint, J=2.2 Hz). □.sub.max (ATR-IR): 655 cm.sup.−1 (br). HRMS (EI): calc'd for C.sub.6H.sub.5F.sub.5Te [M].sup.+: 301.9374, found: 301.9374.

##STR00102##

[0216] The reaction was run according to the general procedure. Clear solid; m.p. 75.4-76.3° C. .sup.19F NMR (282 MHz, CDCl.sub.3): −37.25 (1F, quint, J=151.7 Hz), −52.22 (4F, d, J=151.7 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.88 (2H, d, J=8.7 Hz), 7.71 (2H, dquint, J=8.7, 1.5 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CDCl.sub.3): 142.6, 139.6 (quintd, J=8.5, 2.6 Hz), 131.53 (m), 131.47. □.sub.max (ATR-IR): 656 cm.sup.−1 (br). HRMS (EI): calc'd for C.sub.6H.sub.4ClF.sub.5Te [M].sup.+: 335.8978, found: 335.8967.

##STR00103##

[0217] The reaction was run according to the general procedure. Colorless oil. .sup.19F NMR (377 MHz, CDCl.sub.3): −37.42 (1F, quint, J=152.0 Hz), −51.96 (4F, d, J=152.0 Hz), −57.61 (3F, s); .sup.1H NMR (400 MHz, CDCl.sub.3): 8.01 (2H, d, J=8.9 Hz), 7.55 (2H, dm, J=8.9 Hz); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 154.1 (q, J=2.2 Hz), 138.7 (quintd, J=9.2, 2.9 Hz), 132.6 (quint, J=2.5 Hz), 122.7 (m), 120.1 (q, J=262.2 Hz). □.sub.max (ATR-IR): 672 cm.sup.−1 (br). HRMS (EI): calc'd for C.sub.7H.sub.4OF.sub.8Te [M].sup.+: 385.9191, found: 385.9192.

##STR00104##

[0218] The reaction was run according to the general procedure. Light yellow oil. .sup.19F NMR (282 MHz, CDCl.sub.3): −37.02 (1F, quint, J=151.7 Hz), −51.94 (4F, d, J=151.7 Hz), −98.44 (1F, m); .sup.1H NMR (300 MHz, CDCl.sub.3): 7.97 (2H, dd, J=8.9, 4.7 Hz), 7.43 (2H, m); .sup.13C{.sup.1H} NMR (76 MHz, CDCl.sub.3): 166.5 (d, J=260.1 Hz), 136.6 (m), 133.1 (dquint, J=9.7, 2.5 Hz), 118.8 (dquint, J=23.1, 1.7 Hz). □.sub.max (ATR-IR): 666 cm.sup.−1 (br). HRMS (EI): calc'd for C.sub.6H.sub.4F.sub.6Te [M].sup.4: 319.9274, found: 319.9273.

##STR00105##

[0219] The reaction was run according to the general procedure. Waxy white solid. .sup.19F NMR (377 MHz, CDCl.sub.3): −37.27 (1F, quint, J=151.8 Hz), −52.28 (4F, d, J=151.8 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.87 (2H, dquint, J=8.8, 1.5 Hz), 7.79 (2H, d, J=8.8 Hz); .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3): 140.3 (quintd, J=8.8, 2.9 Hz), 134.4 (m), 131.5 (quint, J=2.3 Hz), 131.1. □.sub.max (ATR-IR): 654 cm.sup.−1 (br). HRMS (EI): calc'd for C.sub.6H.sub.4BrF.sub.5Te [M].sup.+: 379.8473, found: 379.8453.

##STR00106##

[0220] The reaction was run according to the general procedure. Note that we were unable to isolate an analytically pure sample. White solid. .sup.19F NMR (377 MHz, CDCl.sub.3): −36.49 (1F, quint, J=150.8 Hz), −53.11 (4F, d, J=150.8 Hz); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.83 (2H, d, J=8.8 Hz), 7.71 (2H, dquint, J=8.8, 1.7 Hz), 1.37 (9H, s). □.sub.max (ATR-IR): 661 cm.sup.−1 (br). HRMS (EI) calc'd for C.sub.10H.sub.13F.sub.5Te [M].sup.+: 357.9994, found: 357.9987.

##STR00107##

[0221] The reaction was run according to the general procedure. White solid; m.p. 86.2-86.9° C. .sup.19F NMR (377 MHz, CD.sub.3CN): −37.57 (1F, quint, J=148.4 Hz), −54.25 (4F, d, J=148.4 Hz); .sup.1H NMR (400 MHz, CD.sub.3CN): 8.00 (2H, d, J=8.7 Hz), 7.91 (2H, dquint, J=8.7, 1.8 Hz), 4.10-4.02 (2H, m), 3.80-3.71 (2H, m), 1.63 (3H, s); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): 153.5, 141.2 (quintd, J=5.9, 2.9 Hz), 131.2 (quint, J=2.2 Hz), 129.9 (quint, J=1.5 Hz), 108.5, 65.6, 27.4. □.sub.max (ATR-IR): 661 cm.sup.−1 (br). HRMS (EI): calc'd for C.sub.9H.sub.8O.sub.2F.sub.5Te [M]: 372.9501, found: 372.9502.

##STR00108##

[0222] The reaction was run according to the general procedure. Colorless oil. .sup.19F NMR (471 MHz, CD.sub.3CN): −38.42 (1F, quint, J=149.4 Hz), −53.93 (4F, d, J=149.4 Hz), −106.22 (1F, m); .sup.1H NMR (500 MHz, CD.sub.3CN): 7.93-7.84 (3H, m), 7.72-7.69 (3H, m); .sup.13C{.sup.1H}NMR (126 MHz, CD.sub.3CN): 164.0 (dquint, J=255.1, 2.7 Hz), 141.9-141.5 (m), 134.7 (dquint, J=8.2, 1.8 Hz), 127.7-127.6 (m), 124.9 (d, J=20.9 Hz), 118.9 (dm, J=26.3). □.sub.max (ATR-IR): 672 cm.sup.−1 (br).

##STR00109##

[0223] The reaction was run according to the general procedure. White solid; m.p. 127.6-128.6° C. .sup.19F NMR (377 MHz, CD.sub.3CN): −37.64 (1F, quint, J=148.3 Hz), −54.03 (4F, d, J=148.3 Hz), −63.10 (3F, s); .sup.1H NMR (400 MHz, CD.sub.3CN): 8.16-8.10 (4H, m), 7.92 (2H, dm, J=8.4 Hz), 7.87 (2H, dm, J=8.4 Hz). □.sub.max (ATR-IR): 665 cm.sup.−1 (br)

##STR00110##

[0224] The reaction was run according to the general procedure. White solid; m.p. 94.2-96.4° C. .sup.19F NMR (377 MHz, CD.sub.3CN): −38.28 (1F, quint, J=148.6 Hz), −54.16 (4F, d, J=148.6 Hz); .sup.1H NMR (400 MHz, CD.sub.3CN): 8.16 (2H, br d, J=8.6 Hz), 8.10 (2H, dquint, J=8.6, 1.7 Hz), 7.84-7.81 (2H, m), 7.73 (1H, tm, J=7.5 Hz), 7.61-7.56 (2H, m); .sup.13C{H} NMR (101 MHz, CD.sub.3CN): 195.3, 145.4, 144.5-144.2 (m), 136.9, 134.7, 133.3 (quint, J=1.5 Hz), 131.5 (quint, J=2.2 Hz), 131.07, 129.7. □.sub.max (ATR-IR): 1664 cm.sup.−1, 662 cm.sup.−1 (br). HRMS (EI): calc'd for C.sub.13H.sub.9F.sub.5OTe [M].sup.+: 405.9630, found: 405.9632.

##STR00111##

[0225] The reaction was run according to the general procedure. Light yellow oil. .sup.19F NMR (377 MHz, CD3CN): −54.17 (3F, quint, J=21.8 Hz), −68.75 (4F, q, J=21.8 Hz); .sup.1H NMR (400 MHz, CD.sub.3CN): 8.03 (2H, dm, J=8.2 Hz), 7.91 (1H, tm, J=7.5 Hz), 7.86-7.80 (2H, m); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): 142.7 (quint, J=8.6 Hz), 137.0, 132.7, 131.1 (quint, J=2.2 Hz). Note: .sup.13C NMR signal for “CF.sub.3” was not resolved. □.sub.max (ATR-IR): 625 cm.sup.−1 (br).

##STR00112##

[0226] The reaction was run according to the general procedure. .sup.1H NMR (400 MHz, CD.sub.3CN): δ=8.72 (1H, d, J=7.8 Hz), 8.06 (1H, d, J=7.7 Hz), 7.93 (1H, t, J=7.8 Hz), 7.85 (1H, t, J=7.8 Hz); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): δ=140.3, 136.6-136.5 (m), 134.6 (t, J=1.8 Hz), 129.8 (q, J=32.6 Hz), 129.00 (q, J=5.4 Hz), 125.2 (q, J=273.7 Hz), 124.3 (tq, J=14.3, 1.7 Hz); .sup.19F NMR (376 MHz, CD.sub.3CN): δ=−60.36 (3F, s), −161.65 (2F, s).

##STR00113##

[0227] The reaction was run according to the general procedure. .sup.1H NMR (400 MHz, CD.sub.3CN): δ=8.75 (1H, br dd, J=8.7, 5.1 Hz), 7.80 (1H, br d, J=8.7 Hz), 7.56 (1H, br t, J=7.3 Hz); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): δ=165.1 (d, J=256.2 Hz), 143.5 (d, J=9.4 Hz), 133.1 (qd, J=33.7, 8.9 Hz), 123.5 (d, J=22.1 Hz), 123.0 (qd, J=273.9, 2.3 Hz), 119.7-119.1 (m), 117.7 (dq, J=27.0, 5.5 Hz); .sup.19F NMR (376 MHz, CD.sub.3CN): 5=−60.82 (3F, s), −103.17 (1F, s), −159.84 (2F, s).

##STR00114##

[0228] The reaction was run according to the general procedure. H NMR (500 MHz, CD.sub.3CN): δ=8.67 (1H, d, J=8.5 Hz), 8.05 (1H, s.), 7.84 (1H, d, J=8.5 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): =141.9, 140.6, 136.5, 131.8 (q, J=33.2 Hz), 129.6 (q, J=5.4 Hz), 123.2 (q, J=274.2 Hz), 122.2 (tm, J=14.7 Hz); .sup.19F NMR (471 MHz, CD.sub.3CN): δ=−60.77 (3F, s), −160.27 (2F, s)

##STR00115##

[0229] The reaction was run according to the general procedure. H NMR (500 MHz, CD.sub.3CN): δ=8.58 (1H, d, J=8.4 Hz), 8.20 (1H, s), 8.00 (1H, d, J=8.5 Hz.); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN)=141.7, 139.5, 132.3 (q, J=5.3 Hz), 131.6 (q, J=33.1 Hz), 128.7 (t, J=2.1 Hz), 123.0 (q, J=274.3 Hz), 122.9-122.6 (m); .sup.19F NMR (471 MHz, CD.sub.3CN): δ=−60.70 (3F, s), −160.35 (2F, s).

##STR00116##

[0230] The reaction was run according to the general procedure. H NMR (400 MHz, CD.sub.3CN): δ=8.80 (1H, d, J=8.2 Hz), 8.53 (1H, s), 8.37 (1H, d, J=8.2 Hz), 4.42 (2H, q, J=7.0 Hz), 1.39 (3H, t, J=7.1 Hz); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): δ=164.6, 140.7, 136.9, 136.0, 130.4 (q, J=33.2 Hz), 129.4 (q, J=5.3 Hz), 127.4 (t, J=13.9 Hz), 123.5 (q, J=273.8 Hz), 63.2, 14.4; 1.sup.19F NMR (376 MHz, CD.sub.3CN): δ=−60.62 (3F, s), −161.25 (2F, s).

##STR00117##

[0231] The reaction was run according to the general procedure. .sup.1H NMR (500 MHz, CD.sub.3CN): δ=8.93 (1H, br d, J=8.6 Hz), 8.73 (1H, br s), 8.59 (1H, br d, J=8.5 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): =150.8, 141.9, 131.7 (q, J=34.1 Hz), 131.3, 128.3 (t, J=14.4 Hz), 124.5 (q, J=5.5 Hz), 122.9 (q, J=274.3 Hz); .sup.19F NMR (471 MHz, CD.sub.3CN): δ=−60.88 (3F, s), −160.30 (2F, s).

##STR00118##

[0232] The reaction was run according to the general procedure. .sup.1H NMR (500 MHz, CD.sub.3CN): δ=8.16 (1H, d, J=8.2 Hz), 7.95 (1H, d, J=7.8 Hz), 7.87 (1H, t, J=8.2 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): δ=139.7, 136.5, 134.6, 133.0 (q, J=32.3 Hz), 130.2 (t, J=14.3 Hz), 127.5 (q, J=5.7 Hz), 123.6 (q, J=274.3 Hz); .sup.19F NMR (471 MHz, CD.sub.3CN): δ=−60.10 (3F, s), −163.36 (2F, s).

##STR00119##

[0233] The reaction was run according to the general procedure. .sup.1H NMR (500 MHz, CD.sub.3CN): δ=8.33 (1H, d, J=7.8 Hz), 8.22 (1H, d, J=7.9 Hz), 8.00 (1H, t, J=7.9 Hz), 4.03 (3H, s); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): δ=166.6, 135.5, 135.2, 134.8, 132.2 (q, J=5.6 Hz), 131.9 (q, J=32.0 Hz), 124.1 (q, J=274.3 Hz), 123.4 (q, J=14.0 Hz), 54.4; .sup.19F NMR (471 MHz, CD.sub.3CN): 5=−59.23 (3F, s), −159.98 (2F, s).

##STR00120##

[0234] The reaction was run according to the general procedure. .sup.1H NMR (500 MHz, CD.sub.3CN): δ=8.46 (1H, dd, J=8.0, 1.8 Hz), 7.82 (1H, t, J=8.0 Hz), 7.72 (1H, d, J=8.5 Hz), 7.56 (1H, t, J=7.8 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN) 5=146.4 (q, J=1.8 Hz), 137.9, 136.6, 130.5, 123.2 (t, J=13.8 Hz), 121.41 (q, J=259.8 Hz), 121.40 (q, J=1.9 Hz); .sup.19F NMR (471 MHz, CD3CN): δ=−57.60 (3F, s), −166.40 (2F, s).

##STR00121##

[0235] The reaction was run according to the general procedure. .sup.1H NMR (500 MHz, CD3CN): δ=7.80 (1H, t, J=7.7 Hz), 7.37 (2H, br s); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): δ=160.0 (dd, J=253.9, 4.6 Hz), 138.7 (dd, J=11.2, 8.9 Hz), 113.5-113.2 (m), 108.4-107.6 (m); .sup.19F NMR (471 MHz, CD.sub.3CN): δ=−97.43 (2F, br. s), −165.78 (2F, s).

##STR00122##

[0236] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): δ=−124.10 to −124.65 (2F, m), −145.92 (1F, tt, J=19.9, 5.1 Hz), −158.21 to −158.66 (2F, m), −162.08 (2F, s).

##STR00123##

[0237] The reaction was run according to the general procedure. H NMR (500 MHz, CD.sub.3CN): δ=8.37 (1H, dt, J=9.0, 4.6 Hz), 7.34 (1H, td, J=8.9, 2.8 Hz), 7.20 (1H, td, J=8.6, 2.7 Hz); .sup.1H{.sup.19F} NMR (500 MHz, CD.sub.3CN): δ=8.37 (1H, d, J=8.9 Hz), 7.34 (1H, d, J=2.8 Hz), 7.20 (1H, td, J=9.0, 2.8 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): δ=167.0 (ddt, J=256.1, 12.0, 1.9 Hz), 160.4 (dd, J=253.9, 13.3 Hz), 115.5 (dd, J=23.0, 3.4 Hz), 112.2 (dtd, J=23.3, 15.2, 4.5 Hz), 106.3 (t, J=26.8 Hz); .sup.19F NMR (471 MHz, CD.sub.3CN): δ=−94.80 (1F, d, J=11.4 Hz), −101.28 (1F, dt, J=11.1, 4.3 Hz), −165.09 (2F, s).

##STR00124##

[0238] The reaction was run according to the general procedure. .sup.1H NMR (400 MHz, CD.sub.3CN): δ=8.47 (1H, dd, J=8.9, 5.6 Hz), 7.64 (1H, dd, J=8.6, 2.8 Hz), 7.28 (1H, td, J=8.5, 2.8 Hz); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): δ=160.0 (dt, J=256.6, 1.7 Hz), 140.7 (d, J=10.0 Hz), 138.6 (d, J=11.5 Hz), 127.6 (td, J=14.6, 4.0 Hz), 118.8 (t, J=26.7 Hz), 118.3 (t, J=22.7 Hz); .sup.19F NMR (376 MHz, CD.sub.3CN): δ=−103.50 (1F, tq, J=9.3, 4.8 Hz), −164.37 (2F, d, J=4.2 Hz); .sup.19F{.sup.1H} NMR (376 MHz, CD.sub.3CN): δ=−103.50 (1F, t, J=4.5 Hz), −164.37 (2F, d, J=3.7 Hz).

##STR00125##

[0239] The reaction was run according to the general procedure. H NMR (400 MHz, CD.sub.3CN): δ=8.47 (1H, dd, J=8.9, 5.5 Hz), 7.78 (1H, dd, J=8.8, 2.7 Hz), 7.36-7.25 (1H, m); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): δ=165.5 (dt, J=257.4, 1.7 Hz), 141.1 (d, J=9.6 Hz), 130.7 (td, J=14.7, 4.0 Hz), 128.5 (d, J=10.4 Hz), 122.0 (t, J=26.3 Hz), 118.7 (t, J=22.7 Hz); .sup.19F NMR (376 MHz, CD.sub.3CN): δ=−103.74 (1F, br s), −163.35 (2F, br s).

##STR00126##

[0240] The reaction was run according to the general procedure. .sup.1H NMR (400 MHz, CD.sub.3CN): δ=8.32 (1H, dd, J=8.9, 5.5 Hz), 7.34 (1H, dd, J=9.8, 3.0 Hz), 7.12 (1H, td, J=8.6, 3.1 Hz), 2.74 (3H, s); .sup.13C{.sup.1H} NMR (101 MHz, CD.sub.3CN): δ=165.7 (dt, J=252.4, 1.9 Hz), 144.4 (d, J=9.5 Hz), 139.6 (d, J=9.5 Hz), 128.5 (td, J=13.6, 3.0 Hz), 118.9 (t, J=23.1 Hz), 116.8 (t, J=22.8 Hz), 25.1; 1.sup.19F NMR (376 MHz, CD.sub.3CN): δ=−106.86 (1F, tt, J=9.9, 4.8 Hz), −168.31 (2F, d, J=3.7 Hz); .sup.19F{.sup.1H} NMR (376 MHz, CD.sub.3CN): δ=−106.86 (1F, t, J=4.7 Hz), −168.32 (2F, d, J=4.2 Hz).

##STR00127##

[0241] The reaction was run according to the general procedure. .sup.1H NMR (500 MHz, CD.sub.3CN): δ=8.39 (1H, d, J=8.0 Hz), 7.85-7.77 (2H, m), 7.57 (1H, d, J=7.6 Hz), 6.07 (1H, dd, J=46.1, 6.4 Hz), 1.72 (3H, dd, J=24.1, 6.4 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): 141.8 (d, J=20.9 Hz), 137.3, 134.7, 132.4, 129.4 (td, J=13.2, 4.3 Hz), 128.5 (d, J=7.7 Hz), 93.8 (d, J=129.7 Hz), 23.5 (d, J=25.2 Hz); .sup.19F NMR (471 MHz, CD.sub.3CN): 5=−165.35 (2F, s), −165.58 (1F, dq, J=47.8, 24.2 Hz).

##STR00128##

[0242] The reaction was run according to the general procedure. H NMR (500 MHz, CD.sub.3CN): δ=8.42 (1H, d, J=8.0 Hz), 7.85-7.77 (2H, m), 7.61 (1H, br t, J=7.5 Hz), 7.45 (2H, br t, J=6.9 Hz), 7.17 (2H, br t, J=8.5 Hz), 7.02 (1H, d, J=46.1 Hz); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.3CN): δ=163.6 (dd, J=246.6, 2.8 Hz), 139.6 (d, J=23.1 Hz), 138.1 (d, J=28.4 Hz), 137.6, 134.9 (dd, J=22.2, 3.2 Hz), 134.6, 132.8 (d, J=1.8 Hz), 130.6 (dd, J=8.7, 5.8 Hz), 129.7 (d, J=8.6 Hz), 116.6 (d, J=21.9 Hz), 95.4 (d, J=174.0 Hz); .sup.19F NMR (471 MHz, CD.sub.3CN): δ=−113.59 (1F, br. s), −161.74 (1F, d, J=46.2 Hz), −165.69 (2F, br. s)

##STR00129##

[0243] The reaction was run according to the general procedure. H NMR (500 MHz, CD.sub.2Cl.sub.2): δ=8.16 (1H, d, J=8.4 Hz), 7.79 (1H, dd, J=8.4, 2.1 Hz), 5.97 (1H, dt, J=49.3, 3.2 Hz), 3.12-3.05 (1H, m), 2.67-2.54 (1H, m), 2.50-2.41 (1H, m), 2.02-1.95 (2H, m), 1.92-1.82 (1H, m); .sup.13C{.sup.1H} NMR (126 MHz, CD.sub.2Cl.sub.2): 5=142.1, 136.4 (d, J=44.2 Hz), 135.3 (d, J=17.6 Hz), 132.0, 117.0, 88.4 (d, J=170.1 Hz), 31.4, 29.2 (d, J=21.5 Hz), 17.4, 2.1; 1.sup.19F NMR (471 MHz, CD.sub.3CN): δ=−156.94 to −157.21 (1F, m), −165.33 (2F, s)

##STR00130##

[0244] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.31 (2F, qd, J=17.9, 2.0 Hz), −63.19 (3F, t, J=17.9 Hz), −106.82 to −106.95 (1F, m).

##STR00131##

[0245] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.15 (2F, q, J=18.2 Hz), −62.61 (3F, t, J=18.2 Hz), −110.66 to −110.80 (1F, m).

##STR00132##

[0246] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.80 (2F, q, J=18.0 Hz), −62.83 (3F, t, J=18.0 Hz).

##STR00133##

[0247] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.30 (2F, q, J=18.3 Hz), −62.42 (3F, t, J=18.3 Hz).

##STR00134##

[0248] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −11.89 (2F, q, J=18.0 Hz), −61.74 (3F, t, J=18.0 Hz).

##STR00135##

[0249] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.24 (2F, q, J=18.1 Hz), −62.12 (3F, t, J=18.1 Hz).

##STR00136##

[0250] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.22 (2F, q, J=18.3 Hz), −62.11 (3F, t, J=18.3 Hz).

##STR00137##

[0251] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −14.10 (2F, q, J=18.0 Hz), −62.54 (3F, t, J=18.0 Hz).

##STR00138##

[0252] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −4.73 (2F, q, J=17.6 Hz), −59.43 (3F, t, J=17.6 Hz).

##STR00139##

[0253] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.66 (2F, q, J=17.9 Hz), −63.06 (3F, t, J=17.9 Hz).

##STR00140##

[0254] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −13.46 (2F, q, J=18.2 Hz), −62.67 (3F, t, J=18.2 Hz).

##STR00141##

[0255] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −14.06 (2F, q, J=18.3 Hz), −62.80 (3F, t, J=18.3 Hz).

##STR00142##

[0256] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD3CN): −14.50 (2F, q, J=18.3 Hz), −62.91 (3F, t, J=18.3 Hz), −114.82 to −114.97 (1F, m).

##STR00143##

[0257] The reaction was run according to the general procedure. .sup.19F NMR (282 MHz, CD.sub.3CN): −14.36 (2F, q, J=18.0 Hz), −63.62 (3F, t, J=18.0 Hz).