B(C6F5)3催化不饱和烃的硅化反应

doi:10.6023/cjoc202306009

摘要/Abstract

有机硅化合物由于其独特的性质, 在合成化学、药物化学、高分子化学和有机光电材料等领域具有广泛的应用. 不饱和化合物的硅化反应是获得有机硅化合物的重要途径之一, 因此引起了化学家的关注并取得了令人瞩目的进展. B(C₆F₅)₃作为一类独特的非金属路易斯酸, 近年来, 其催化不饱和烃的硅化取得了重要的研究进展, 详细介绍了不饱和烃的硅化反应及机理研究.

关键词: 路易斯酸, 硅化反应, 硅氢化反应, 不饱和烃

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

引用此文

冯向青, 杜海峰. B(C₆F₅)₃催化不饱和烃的硅化反应[J]. 有机化学, 2023, 43(10): 3544-3557.

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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图/表 35

图式1. 取代烯烃的硅氢化反应

Scheme 1. Hydrosilylation of substituted alkenes

图式2. 烯烃硅氢化反应的机理

Scheme 2. Mechanism for the hydrosilylation of alkenes

图式3. B(C6F5)3催化的烯烃的转移硅氢化反应

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

图式4. B(C6F5)3催化烯烃的转移硅氢化反应

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

图式5. 甲硅烷替代物对C=C双键的转移硅氢化反应

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

图式6. 共轭腈的硅氢化反应

Scheme 6. Silylative reduction of conjugated nitriles

图式7. 硼烷催化硅氢化还原共轭腈的机理

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

图式8. 共轭腈部分还原为烯胺

Scheme 8. Partial reduction of conjugated nitriles to enamines

图式9. α,β-不饱和酯和烯酰胺的硅氢化反应

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

图式10. 内酯和内酰胺的α-硅烷化

Scheme 10. α-Silylation of lactones and lactams

图式11. α,β-不饱和醛的硅烷化还原胺化反应

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

图式12. α,β-不饱和醛亚胺的硅烷化还原

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

图式13. B(C6F5)3催化炔烃的转移硅氢化反应

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

图式14. B(C6F5)3/胺催化末端炔烃硅基化反应

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

图式15. 三(五氟苯基)硼烷催化硅烷化联苯的脱氢硅化反应

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

图式16. 炔烃的一锅硅氢化/脱氢硅化形成硅烷茚

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

图式17. 取代苯胺衍生物的C—H硅烷化反应

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

图式18. 代表性硅烷化产物的合成应用

Scheme 18. Synthetic applications of some representative silylation products

图式19. 硼催化C—H硅烷化的可能机理

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

图式20. 喹啉的催化硅烷化还原

Scheme 20. Catalytic silylative reduction of quinolines

图式21. 吡啶的硅烷化还原

Scheme 21. Silylative reduction of pyridines

图式23. B(C6F5)3催化的脱氢/氢化硅化反应

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

图式22. 杂芳烃的亲电官能化

Scheme 22. Electrophilic functionalisation of heteroarenes

图式24. 吲哚的歧化反应

Scheme 24. Disproportionation reaction of indoles

图式25. 硼烷催化2-取代呋喃的开环和关环串联反应

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

图式26. B(C6F5)3催化呋喃和苯并呋喃衍生物的硅烷基化开环反应

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

图式27. B(C6F5)3催化的氢化硅烷的选择性取代基再分布

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

图式28. B(C6F5)3催化氢化硅烷的C—Si/Si—H交叉复分解反应

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

图式29. B(C6F5)3催化硅烷交叉复分解反应

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

图式30. 哌啶的串联硅烷基化

Scheme 30. Cascade silylation of piperidines

图式31. 串联硅烷化反应的催化途径

Scheme 31. Proposed catalytic pathway for cascade silylation

图式32. 乙烯基环丙烷的硅氢化反应

Scheme 32. Hydrosilylation of vinylcyclopropanes

图式33. 乙烯基环丙烷的硅氢化反应机理

Scheme 33. Reaction mechanism of the hydrosilylation of vinylcyclopropanes

图式34. 乙烯基环丙烷和Et2SiH2的形式上的[4＋1]环加成反应

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

图式35. 形式上的[4＋1]环加成反应机理

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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