B(C6F5)3-Catalyzed Silylation of Unsaturated Hydrocarbons

doi:10.6023/cjoc202306009

Abstract

Organosilicon compounds have been widely applied in synthetic chemistry, medicinal chemistry, polymer chemistry, organic photoelectric materials and other fields due to their unique properties. The silylation of unsaturated compounds represents one of the most important approaches for the synthesis of organosilicon compounds, which has attracted the intensive attention of chemists, and a great success has been achieved. As a unique non-metallic Lewis acid, B(C₆F₅)₃-catalyzed silylation of unsaturated compounds has made a significant progress in recent years. This subject and the corresponding mechanism are demonstrated.

Key words: Lewis acids, silylation reaction, hydrosilylation reaction, unsaturated hydrocarbons

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Xiangqing Feng, Haifeng Du. B(C₆F₅)₃-Catalyzed Silylation of Unsaturated Hydrocarbons[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3544-3557.

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Fig. & Tab. 35

Scheme 1. Hydrosilylation of substituted alkenes

Scheme 2. Mechanism for the hydrosilylation of alkenes

Scheme 3. B(C6F5)3-catalyzed transfer hydrosilylation of various alkenes

Scheme 4. B(C6F5)3-catalyzed transfer hydrosilylation of alkene 8a

Scheme 5. Transfer hydrosilylation of C=C multiple bonds with SiH4 surrogate

Scheme 6. Silylative reduction of conjugated nitriles

Scheme 7. Proposed mechanism for the borane-catalyzed silylative reduction of conjugated nitriles

Scheme 8. Partial reduction of conjugated nitriles to enamines

Scheme 9. Hydrosilylations of α,β-unsaturated esters and enamides

Scheme 10. α-Silylation of lactones and lactams

Scheme 11. Silylative reductive amination of α,β-unsaturated aldehydes

Scheme 12. Silylative reduction of α,β-unsaturated aldimines

Scheme 13. B(C6F5)3-catalyzed transfer hydrosilylation of alkyne

Scheme 14. B(C6F5)3/amine-catalyzed silylation of terminal alkynes

Scheme 15. Dehydrosilylation of silylated biphenyls with B(C6F5)3

Scheme 16. One-pot hydrosilylation/dehydrosilylation of alkynes to form silaindenes

Scheme 17. C—H silylation of various substituted aniline derivatives

Scheme 18. Synthetic applications of some representative silylation products

Scheme 19. Possible mechanism for boron-catalyzed C—H silylation

Scheme 20. Catalytic silylative reduction of quinolines

Scheme 21. Silylative reduction of pyridines

Scheme 23. Dehydro-/hydrosilylation catalyzed by B(C6F5)3

Scheme 22. Electrophilic functionalisation of heteroarenes

Scheme 24. Disproportionation reaction of indoles

Scheme 25. Silylative ring-opening of 2-substituted furans

Scheme 26. Borane catalyzed silylative ring opening and closing cascades of 2-substituted furans

Scheme 27. B(C6F5)3-catalyzed selective substituent redistribution of hydrosilanes

Scheme 28. B(C6F5)3-catalyzed C—Si/Si—H cross-metathesis of hydrosilanes

Scheme 29. B(C6F5)3-catalyzed cross-metathesis of hydrosilanes

Scheme 30. Cascade silylation of piperidines

Scheme 31. Proposed catalytic pathway for cascade silylation

Scheme 32. Hydrosilylation of vinylcyclopropanes

Scheme 33. Reaction mechanism of the hydrosilylation of vinylcyclopropanes

Scheme 34. Formal [4＋1] cycloaddition of VCPs and Et2SiH2

Scheme 35. Mechanism of the formal [4＋1] cycloaddition

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B(C₆F₅)₃催化不饱和烃的硅化反应

B(C₆F₅)₃-Catalyzed Silylation of Unsaturated Hydrocarbons

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Fig. & Tab. 35

References 29

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B(C6F5)3催化不饱和烃的硅化反应