Claims
- 1. A method for generating a carbon-carbon bond between a transferable group and an acceptor group which comprises the steps of:
a. reacting a organosilicon reagent of the formula: 206where T is the transferable group that can be selected from an aromatic group, a substituted aromatic group, a heteroaromatic group, an olefinic group, a substituted olefinic group, an allylic group, a substituted allylic group, an acetylenic group, a substituted acetylenic group, an allenic group, a substituted allenic group, an alkyl group, and a substituted alkyl group; X is selected from the group consisting of a hydrogen, an alkyl group, a substituted alkyl group, an olefinic group, a substituted olefinic group, an acetylenic group, a substituted acetylenic group, an aromatic group, a substituted aromatic group, a heteroaromatic group, a halide, OR or N(R)2 groups, where R is hydrogen, an alkyl group or a substituted alkyl group, and a silane or siloxane group; R1 and R2 are, independently, selected from the group consisting of alkyl or substituted alkyl groups, a silane group or a siloxane group; and where dashed lines indicate that any two of R1, R2, T or X can be covalently linked and R1 and R2 can be a transferable group T; with an organic electrophile in the presence of a basic and nucleophilic activator anion and a Group 10 metal catalyst; and b. recovering the desired cross-coupling product T-R3 in which the —C—C— bond is formed.
- 2. The method of claim 1 wherein the organosilicon nucleophile is an alkenylsilacycloalkane.
- 3. The method of claim 1 wherein the organosilicon nucleophile is an aryl(fluoro)silacycloalkane or an aryl(chloro)silacycloalkane.
- 4. The method of claim 4 wherein the organosilicon nucleophile is an aryl(fluoro)silacyclobutane or an aryl(chloro)silacyclobutane.
- 5. The method of claim 1 wherein the organosilicon nucleophile is an aromatic or alkenylsilanol.
- 6. The method of claim 1 wherein the organosilicon nucleophile is a siloxane.
- 7. The method of claim 1 wherein the organosilicon nucleophile is a bis-silyl compound.
- 8. The method of claim 1 wherein the organic electrophile is a compound of formula R3Y, where Y is a leaving group and R3 is the acceptor group which is selected from the group consisting of an aromatic group, a substituted aromatic group, a heteroaromatic group, an olefinic group, a substituted olefinic group, an allylic group, a substituted allylic group, an acetylenic group, a substituted acetylenic group, an allenic group, a substituted allenic group, an alkyl group, and a substituted alkyl group.
- 9. The method of claim 1 further comprising the step of combining the organosilicon nucleophile with the activator anion to activate the organosilicon nucleophile before it is reacted with the organic electrophile.
- 10. The method of claim 9 wherein the activator anion is present in molar equivalents in an amount ranging from about 2 to 3 times that of the organosilicon nucleophile.
- 11. The method of claim 8 wherein the acceptor is an alkenyl group or a substituted alkenyl group.
- 12. The method of claim 8 wherein the acceptor is an aromatic group or a substituted aromatic group.
- 13. The method of claim 8 wherein the acceptor is a heteroaromatic group.
- 14. The method of claim 1 wherein the organosilicon nucleophile has the formula:
- 15. The method of claim 14 wherein T is an alkenyl group or a substituted alkenyl group.
- 16. The method of claim 14 wherein T is an aromatic group, a substituted aromatic group or a heteroaromatic group.
- 17. The method of claim 14 where r is 1.
- 18. The method of claim 1 wherein the organosilicon nucleophile has the formula:
- 19. The method of claim 18 wherein T is an aromatic group, a substituted aromatic group or a heteroaromatic group.
- 20. The method of claim 1 wherein T is an alkenyl, substituted alkenyl, aromatic group or substituted aromatic group and X is OH.
- 21. The method of claim 1 wherein the organosilicon nucleophile has the formula:
- 22. The method of claim 21 wherein the organosilicon nucleophile has the formula:
- 23. The method of claim 22 wherein T is an alkenyl, dienyl, allyl, or acetylenic group.
- 24. The method of claim 21 wherein n is 1-5, inclusive.
- 25. The method of claim 1 wherein the organosilicon nucleophile is:
- 26. The method of claim 25 having the formula:
- 27. The method of claim 26 wherein one or more R1 or R2 groups are transferrable groups.
- 28. The method of claim 1 wherein the organosilicon nucleophile has the formula:
- 29. The method of claim 28 wherein one or more of R1, R2, RA or RB is a transferable group.
- 30. The method of claim 28 wherein the organosilicon nucleophile has the formula:
- 30. The method of claim 29 wherein T is an olefin or a substituted olefin.
- 31. The method of claim 1 wherein the T group is substituted with a siloxane group.
- 32. The method of claim 1 wherein the T group is substituted with a silane group.
- 33. The method of claim 28 wherein the organosilicon nucleophile has the formula:
- 34. The method of claim 33 wherein T is an olefin.
- 35. The method of claim 33 wherein T is a vinyl group.
- 36. The method of claim 28 wherein the organosilicon nucleophile has the formula:
- 37. The method of claim 36 wherein T is an olefin.
- 38. The method of claim 36 wherein T is a vinyl group.
- 39. The method of claim I wherein the organosilicon nucleophile has the formula:
- 40. The method of claim 39 wherein T is an olefin or a substituted olefin.
- 41. The method of claim 1 wherein the activator is a tetraalkylammonium fluoride, tetraalkylammonium hydroxide, or a tetraalkylammonium alkoxide.
- 42. The method of claim 1 wherein the activator is a tetrabutylammonium fluoride, tetrabutylammonium hydroxide, or a tetrabutylammonium alkoxide
- 43. The method of claim 1 wherein the palladium catalyst is selected from the group consisting of Pd(dba)2; Pd(dba)3; [Pd(allyl)Cl]2; PdCl2; Pd(OAc)2; Pd(OTFA)2; (COD)PdBr2; Pd(OTf)2; and (PhCN)2PdCl2.
- 44. The method of claim 1 wherein the palladium catalyst is Pd(dba)2 or [Pd(allyl)Cl]2.
- 45. The method of claim 1 wherein the reaction is carried out in a polar aprotic solvent.
- 46. The method of claim 1 wherein the organosilicon nucleophile is activated prior to reaction with the organic electrophile.
- 47. The method of claim 1 wherein the reaction is carried out at ambient temperature.
- 48. The method of claim 1 wherein in T groups that contain —CH2— groups one or more non-neighboring —CH2— groups can be replaced with —O—; —S—; —NH—; —NH—CO—; —NR—, or —NR—CO—, where R is alkyl; —C═O; or —O—C═O.
- 49. The method of claim 1 wherein the T group is substituted with one or more groups selected from a halide; and acyl group; an OR or N(R)2 group, where R is a hydrogen, an alkyl or aryl group; an SR′ group, where R′ is an alkyl, aryl group, a substituted alkyl group, or a substituted aryl group.
- 50. The method of claim 1 wherein the organosilicon nucleophile is an alkenyl silanol.
- 51. The method of claim 50 wherein the activator anion is hydride.
- 52. The method of claim 50 wherein the activator anion is a trialkyl silanolate.
- 53. The method of claim 52 wherein the activator anion is trimethyl silanolate.
- 54. The method of claim 50 wherein the activator is fluoride-free.
- 55. The method of claim 54 wherein the method is carried out in DMF or DME.
- 56. The method of claim 1 wherein the organosilicon nucleophile has the formula:
- 57. The method of claim 56 wherein the organonucleophile has the formula:
- 58. The method of claim 57 wherein the organosilicon nucleophile has the formula:
- 59. The method of claim 56 wherein the organoelectrophile is an aryl halide or a substituted aryl halide.
- 60. The method of claim 56 wherein the organoelectrophile is an olefin or a substituted olefin.
- 61. The method of claim 56 wherein the organonucleophile has the formula:
- 62. The method of claim 61 wherein the organoelectrophile is an aryl halide or substituted aryl halide.
- 63. The method of claim 62 wherein the organoelectrophile is an olefin or a substituted olefin.
- 64. The method of claim 61 further comprising the step of forming the organosilicon nucleophile by intramolecular hydrosilylation of a homopropargyl alcohol.
- 65. The method of claim 64 wherein the intramolecular hydrosilylation is catalyzed by a platinum catalyst.
- 66. The method of claim 65 wherein the catalyst is H2PtCl2 or Pt(DVDS).
- 67. The method of claim 64 wherein the intramolecular hydrosilyation and the cross-coupling reactions are performed in the same reaction vessel without purification of intermediates.
- 68. The method of claim 1 wherein the organosilicon nucleophile has the formula:
- 69. The method of claim 68 wherein n is 1 and R′ are all hydrogens.
- 70. The method of claim 68 wherein the organosilicon nucleophile is formed by ring-closing metathesis.
- 71. The method of claim 70 wherein the ring-closing metathesis is catalyzed by a Mo catalyst.
- 72. A method for hydrocarbation of terminal alkynes to form a derivatized olefin which comprises the steps of:
(a) hydrosilylation of the terminal alkyne in the presence of a Pt catalyst; (b) reaction of the hydrosilyation product of step a with an organic electrophile in the presence of an basic and nucleophilic activator ion and a Group 10 metal catalyst; (c) recovery of the derivatized olefin product of hydrocarbation.
- 73. A method of claim 72 wherein the terminal alkyne is hydrosilylated with a dialkylchlorosilane in the presence of a Pt catalyst followed by in situ hydrolysis.
- 74. The method of claim 72 wherein the Pt catalyst is H2PtCl6.
- 75. The method of claim 72 wherein the organic electrophile comprises an aryl or olefinic group.
- 76. The method of claim 72 wherein the activator ion is F−.
- 77. The method of claim 72 wherein the Group 10 metal catalyst is a Pd catalyst.
- 78. The method of claim 77 wherein the Pd catalyst is Pd (dba)2.
- 79. The method of claim 72 wherein the terminal alkyne is hydrosilylated by reaction with a hydrodisiloxane.
- 80. The method of claim 73 wherein the Pt catalyst is H2PtCl6, Pt(DVDS) complex or t-Bu3P-modified Pt(DVDS) complex.
- 81. The method of claim 72 wherein the organic electrophile comprises an aryl group or an olefinic group.
- 82. The method of claim 72 wherein the activator ion is F−.
- 83. The method of claim 72 wherein the Group 10 initial catalyst is a Pd catalyst.
- 84. The method of claim 83 wherein the Pd catalyst is Pd (dba)2.
- 85. A reagent for formation of a —C—C— bond which comprises an organosilicon nucleophile of formula:
- 86. The reagent of claim 85 for the cross-coupling of an olefin substrate and an aryl group wherein the T group in the organosilicon nucleophile is a an olefinic group, a substituted olefinic group, an allylic group, or a substituted allylic group.
- 87. The reagent of claim 85 for the cross-coupling of an aryl group with an olefin substrate wherein the T group of the organosilicon nucleophile is an aromatic group, a substituted aromatic group, or a heteroaromatic group.
- 88. A kit for performing a cross-coupling reaction which comprises one or more organosilicon nucleophiles of formula:
- 89. The kit of claim 88 further comprising an activating anion.
- 90. The kit of claim 89 further comprising a Pd catalyst for the cross-coupling reaction.
- 91. The kit of claim 88 wherein the organosilicon reagent is a siloxane.
- 92. The kit of claim 91 wherein the organosilicon reagent is a cyclic siloxane.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application takes priority under 35 U.S.C. 119(e) from U.S. provisional application Serial No. 60/209,682, filed Jun. 6, 2000 which is incorporated in its entirety by reference herein.
STATEMENT OF FEDERAL SUPPORT
[0002] This invention was funded by the United States government through a National Science Foundation grant NSF CHO 9803124 and 9500397. The United States government has certain rights in this invention.
Provisional Applications (1)
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Number |
Date |
Country |
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60209682 |
Jun 2000 |
US |