有机硅金属试剂在碳硅交叉偶联应用研究进展

doi:10.6023/cjoc201904024

摘要/Abstract

有机硅化合物因其特殊的性质广泛应用于合成化学、医药、农药和材料等领域.有机硅化合物通常由亲核取代、烯烃硅氢化和碳氢键直接硅化等方法制备.近年来，交叉偶联构建碳硅键，特别是构建C（sp³）-Si键取得突破性进展，引起广泛关注和兴趣，成为有机硅化合物合成研究热点.从极性反转的硅亲核试剂即有机硅金属试剂角度，总结近些年来有机硅金属试剂参与交叉偶联合成有机硅烷研究进展.有机硅硼试剂、有机硅镁试剂、有机硅锌试剂、联硅试剂、有机硅铝试剂和有机硅锂试剂等六方面总结各类金属试剂在碳硅键偶联的进展.

关键词: 有机硅金属试剂, 交叉偶联, 过渡金属催化, 有机硅化合物

Organosilanes have been widely applied in synthetic chemistry, pharmaceuticals, agrochemicals, and materials due to the special properties. Several synthetic strategies including nucleophilic substitution, hydrosilylation of alkene, and C-H silylation have been developed. In recent years, significant progress has advanced in the cross-coupling of C-Si bond for the synthesis of organosilanes, especially in the break-through of the cross-coupling of C(sp³)-Si bond. It has become one of the hottest issues in synthetic chemistry. The recent progress on the cross-coupling of C-Si bond by using silyl reagents is summarized. The application of silyl reagents in cross-coupling for C-Si bond formation including silyl boranes, organosilyl magnesium, organosilyl zinc, unasymetric disilanes, organosilyl aluminum and organosilyl lithium reagents is mainly discussed.

Key words: silyl reagents, cross-coupling, transition-metal catalysis, organosilanes

引用此文

王明凤, 余茂栋, 王文蜀, 林伟立, 罗斐贤. 有机硅金属试剂在碳硅交叉偶联应用研究进展[J]. 有机化学, 2019, 39(11): 3145-3153.

Wang Mingfeng, Yu Maodong, Wang Wenshu, Lin Weili, Luo Feixian. Cross-Coupling of C-Si Bond by Using Silyl Reagents[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3145-3153.

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图/表 24

图式 1. 交叉偶联构建碳硅键

Scheme 1. Cross-coupling of Si—C bond

图式 2. Ni/Cu催化特戊酸酯碳氧键活化硅化反应

Scheme 2. Ni/Cu-catalyzed silylation of pivalate via C—O activation

图式 3. Ni催化碳氧键硅化反应机理

Scheme 3. Mechanism of Ni catalyzed silylation of C—O bond

图式 4. 镍催化芳甲醚与有机硅硼试剂交叉偶联

Scheme 4. Ni-catalyzed cross-coupling of methoxyl aromatics and silyl boranes

图式 5. Pd催化卤代芳烃与有机硅硼试剂交叉偶联

Scheme 5. Pd-catalyzed cross-coupling of aromatic halides and silyl boranes

图式 6. 氟代烃脱氟硅化反应

Scheme 6. Defluorosilylation of fluoroarenes and fluoroalkanes

图式 7. 偕二氟烯烃脱氟硅化反应

Scheme 7. Defluorosilylation of gem-difluoroalkenes

图式 8. 碱促进的氟代烃脱氟硅化反应

Scheme 8. Base promoted defluorosilylation of fluoroarenes and fluoroalkanes

图式 9. 镍/铜协同催化酯的脱羰硅化反应

Scheme 9. Ni/Cu-catalyzed decarbonylative silylation of esters

图式 10. Pd催化卤代苄与有机硅硼试剂交叉偶联

Scheme 10. Pd-catalyzed cross-coupling of benzylic halides and silyl boranes

图式 11. 铜催化烷基三氟甲磺酸酯与有机硅硼试剂交叉偶联

Scheme 11. Cu-catalyzed cross-coupling of alkyl aliphatic triflates and silyl boranes

图式 12. 铜催化烷基碘代物与有机硅硼试剂交叉偶联

Scheme 12. Cu-catalyzed cross-coupling of alkyl iodides and silyl boranes

图式 13. 铜催化烷基羧酸衍生物与有机硅硼试剂交叉偶联

Scheme 13. Cu-catalyzed cross-coupling of aliphatic carboxylic acid derivatives and silyl boranes

图式 14. 铜催化烷α-三氟甲磺酰氧取代脂肪腈或酸酯与有机硅硼试剂交叉偶联

Scheme 14. Cu-catalyzed cross-coupling of α-triflyloxy nitriles or esters and silyl boranes

图式 15. 钯催化烯基或烯丙基磷酸酯与有机硅镁试剂交叉偶联

Scheme 15. Pd-catalyzed cross-coupling of allylic or vinyl phosphates and organosilyl magnesium reagents

图式 16. 铁或钴催化溴代烷烃与有机硅镁试剂交叉偶联

Scheme 16. Fe/Co-catalyzed cross-coupling of alkyl bromides and organosilyl magnesium reagents

图式 17. 铜催化烯丙基碳酸酯或氨基甲酸酯与有机硅锌试剂交叉偶联

Scheme 17. Cu-catalyzed cross-coupling of allylic esters or carbamates and organosilyl zinc reagents

图式 18. 镍催化烷基溴代物与有机硅锌试剂交叉偶联

Scheme 18. Ni-catalyzed cross-coupling of alkyl bromides and organosilyl zinc reagents

图式 19. 铜催化烷基溴代物与有机硅锌试剂交叉偶联

Scheme 19. Cu-catalyzed cross-coupling of vinyliodonium salts and organosilyl zinc reagents

图式 20. 铑催化芳基氰化物与联硅烷交叉偶联

Scheme 20. Rh-catalyzed cross-coupling of nitriles and disilanes

图式 21. 钯催化氯代芳烃与不对称联硅试剂交叉偶联

Scheme 21. Pd-catalyzed cross-coupling of aromatic chlorides and silylsilatranes

图式 22. 钯催化磷酸酯与有机硅铝试剂交叉偶联

Scheme 22. Pd-catalyzed cross-coupling of vinyl or allyl phosphates and organosilyl aluminum reagents

图式 23. 钯催化溴代芳烃或碘代烯烃与有机硅铝试剂交叉偶联

Scheme 23. Pd-catalyzed cross-coupling of aromatic bromides or vinyl iodides and organosilyl aluminum reagents

图式 24. 溴代芳烃或碘代烯烃与有机硅锂试剂交叉偶联

Scheme 24. Cross-coupling of aromatic bromides or vinyl iodides and organosilyl lithium reagents

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