ORGANOMETAL BENZENEPHOSPHONATE COUPLING AGENTS

1 . A compound of formula I

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, phenyl, benzyl, Group 1 salts, Group 2 salts, and ammonium salts; and

R 3 is selected from the group consisting of

ZnX wherein X is halogen; and

B(OR 4 )(OR 5 ), wherein R 4 and R 5 are independently selected from H and (C 1 -C 6 ) alkyl, or R 4 and R 5 together form a 5-6 membered ring.

2 . The compound according to claim 1 wherein R 3 is B(OR 4 )(OR 5 ), of formula:

3 . The compound according to claim 2 wherein R 1 , R 2 , R 4 and R 5 are H, of formula:

4 . The compound according to claim 2 wherein R 4 and R 5 together form a 5-membered saturated ring, of formula:

wherein

R 6 , R 7 , R 8 and R 9 are independently selected from H and (C 1 -C 6 ) alkyl.

5 . The compound according to claim 4 wherein R 1 , R 2 , R 6 , R 7 , R 8 and R 9 are methyl, of formula:

6 . The compound according to claim 4 wherein R 1 and R 2 are H; and R 6 , R 7 , R 8 and R 9 are methyl, of formula:

7 . The compound according to claim 2 wherein R 4 and R 5 together form a 6-membered saturated ring, of formula:

wherein R 6 , R 7 , R 8 and R 9 are independently selected from H and (C 1 -C 6 ) alkyl.

8 . A compound according to claim 2 wherein R 4 and R 5 together form a 6-membered saturated ring, of formula:

wherein R 7 and R 8 are independently selected from H and (C 1 -C 6 ) alkyl.

9 . The compound of claim 8 wherein R 1 and R 2 are ethyl; and R 7 and R 8 are methyl, of formula:

10 . The compound according to claim 1 wherein R 3 is ZnX, of formula:

11 . The compound according to claim 10 wherein R 1 and R 2 are CH 3 .

12 . A compound of formula II:

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl; and

R 3a is Sn(R 10 )(R 11 )(R 12 ) wherein R 10 , R 11 and R 12 are each (C 1 -C 8 ) alkyl.

13 . The compound according to claim 12 wherein R 1 and R 2 are independently selected from H, methyl and ethyl.

14 . The compound according to claim 12 , wherein R 10 , R 11 and R 12 are n-butyl, of formula:

15 . A compound of formula III:

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl; and

R 3b is Si(R 13 )(R 14 )(R 15 ) wherein R 13 is selected from OH and (C 1 -C 6 ) alkoxy; R 14 and R 15 are independently selected from (C 1 -C 6 ) hydrocarbon and (C 1 -C 6 ) alkoxy;

with the proviso that when R 1 and R 2 are both CH 2 CH 3 , then R 13 , R 14 and R 15 are other than ethyloxy.

16 . The compound according to claim 15 wherein R 1 and R 2 are independently selected from H, methyl and ethyl.

17 . The compound according to claim 15 wherein R 13 , R 14 and R 15 are OCH 3 .

18 . The compound according to claim 15 wherein R 13 is OCH 3 ; and R 14 and R 15 are CH 3 .

19 . The compound according to claim 16 wherein R 1 and R 2 are ethyl, R 13 is OH; and R 14 and R 15 are CH 3 of formula:

20 . A compound of formula IV

(IV)

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl; and

R 3c is [Si(R 16 )(R 17 )(R 18 )X] − M + wherein R 16 is OH or (C 1 -C 6 ) alkoxy; R 17 and R 18 are independently selected from H, OH, (C 1 -C 6 ) hydrocarbon and (C 1 -C 6 ) alkoxy; X is selected from the group consisting of F, OAc, OR, OSiCH 3 ; M + is a counterion and R is selected from (C 1 -C 6 ) alkyl.

21 . The compound according to claim 20 wherein R 16 , R 17 and R 18 are OCH 3 .

22 . The compound according to claim 20 wherein R 16 is OCH 3 ; and R 17 and R 18 are CH 3 .

23 . A compound of formula V

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl; and

R 3e is [Sn(R 19 )(R 20 )(R 21 )X] − M + wherein R 19 , R 20 and R 21 are independently selected from (C 1 -C 8 ) alkyl; and X is selected from the group consisting of halogen, OAc, OR, and OSiCH 3 wherein R is selected from (C 1 -C 6 ) alkyl and M + is a counterion.

24 . The compound according to claim 23 wherein R 19 , R 20 and R 21 are C 4 H 9 .

25 . (canceled)

26 . (canceled)

27 . (canceled)

28 . A method of generating a carbon-carbon bond comprising reacting a compound according to claim 1 with an organic electrophile selected from an aryl halide, aryl triflate and aryl sulfonate; in the presence of a metal catalyst selected from a Group 8, Group 9 and Group 10 metal.

29 . A method of generating a carbon-carbon bond, comprising reacting a compound of formula

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl;

and R 3d is Si (R 19 )(R 20 )(R 21 ) wherein R 19 is selected from OH and (C 1 -C 6 ) alkoxy; and R 20 and R 21 are independently selected from H, (C 1 -C 6 ) hydrocarbon and (C 1 -C 6 ) alkoxy;

with an organic electrophile selected from an aryl halide, aryl triflate and aryl sulfonate;

in the presence of a metal catalyst selected from a Group 8, Group 9 and Group 10 metal.

30 . (canceled)

31 . A method of generating a carbon-carbon bond, comprising reacting a compound of formula

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, phenyl, benzyl, Group 1 salts, Group 2 salts, and ammonium salts;

R 3 is selected from the group consisting of

ZnX wherein X is halogen; and

B(OR 4 )(OR 5 ), wherein R 4 and R 5 are independently selected from H and (C 1 -C 6 ) alkyl, or R 4 and R 5 together form a 5-6 membered ring;

with an organic electrophile selected from an aryl halide, aryl triflate and aryl sulfonate;

in the presence of a metal catalyst selected from a Group 8, Group 9 and Group 10 metal.

32 . A method of generating a carbon-carbon bond, comprising reacting a compound of formula

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl; and

R 3a is Sn(R 10 )(R 11 )(R 12 ) wherein R 10 , R 11 and R 12 are each (C 1 -C 8 ) alkyl;

with an organic electrophile selected from an aryl halide, aryl triflate and aryl sulfonate;

in the presence of a metal catalyst selected from a Group 8, Group 9 and Group 10 metal.

33 . A method of generating a carbon-carbon bond, comprising reacting a compound of formula

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl; and

R 3c is [Si(R 16 )(R 17 )(R 18 )X] − M + wherein R 16 is OH or (C 1 -C 6 ) alkoxy; R 17 and R 18 are independently selected from H, OH, (C 1 -C 6 ) hydrocarbon and (C 1 -C 6 ) alkoxy; X is selected from the group consisting of F, OAc, OR, OSiCH 3 ; M + is a counterion and R is selected from (C 1 -C 6 ) alkyl.

with an organic electrophile selected from an aryl halide, aryl triflate and aryl sulfonate;

in the presence of a metal catalyst selected from a Group 8, Group 9 and Group 10 metal.

34 . A method of generating a carbon-carbon bond, comprising reacting a compound of formula

wherein

R 1 and R 2 are independently selected from H, (C 1 -C 6 ) alkyl, benzyl and phenyl; and

R 3e is [Sn(R 19 )(R 20 )(R 21 )X] − M + wherein R 19 , R 20 and R 21 are independently selected from (C 1 -C 8 ) alkyl; and X is selected from the group consisting of halogen, OAc, OR, and OSiCH 3 wherein R is selected from (C 1 -C 6 ) alkyl and M + is a counterion;

with an organic electrophile selected from an aryl halide, aryl triflate and aryl sulfonate;

in the presence of a metal catalyst selected from a Group 8, Group 9 and Group 10 metal.

35 . (canceled)

36 . (canceled)

37 . (canceled)

38 . (canceled)

39 . The method of either of claims 28 or 31 wherein the metal catalyst is a Group 10 metal.

40 . The method of claim 39 wherein the Group 10 metal catalyst is selected from nickel, platinum and palladium.

41 . The method of claim 40 wherein the Group 10 metal catalyst is palladium.

42 . The method of either of claims 32 or 34 wherein the metal catalyst is a Group 10 metal.

43 . The method of claim 42 wherein the Group 10 metal catalyst is selected from nickel, platinum and palladium.

44 . The method of claim 43 wherein the Group 10 metal catalyst is palladium.

45 . The method of either of claims 29 or 33 wherein the metal catalyst is a Group 10 metal.

46 . The method of claim 45 wherein the Group 10 metal catalyst is selected from nickel, platinum and palladium.

47 . The method of claim 46 wherein the Group 10 metal catalyst is palladium.