离子转移反应的研究进展

doi:10.6023/cjoc202211047

摘要/Abstract

近年来, 一类新颖的名为“离子转移反应”的有机化学反应受到人们的广泛关注. 这类反应拥有独特的反应机理, 可以避免易燃易爆、剧毒等不易操作试剂的使用, 为不饱和化合物的转移官能团化, 例如转移氢硅化、转移氢化、转移氢卤化和转移氢氰化等提供了新型强有力的工具. 对近年来报道的离子转移反应以及相关的反应机理进行了总结, 同时对该领域的未来发展方向进行了展望.

关键词: 离子转移反应, 转移氢官能团化, 烯烃, 加成反应, 催化

In recent years, a series of novel organic reactions, named “ionic transfer reaction”, has received much attention. This kind of reaction has a characteristic mechanism and avoids the use of inflammable, explosive, highly toxic and other difficult to operate reagents. It provides a new powerful tool for transfer functionalizations of unsaturated compounds, such as transfer hydrosilylations, transfer hydrogenations, transfer hydrohalogenations, and transfer hydrocyanations. Herein, the recent progress of ionic transfer reactions and related mechanisms are summarized. Furthermore, the future developments of ionic transfer reactions are prospected.

Key words: ionic transfer reaction, transfer hydrofunctionalization, olefins, addition reaction, catalysis

引用此文

李落墨, 杨小会. 离子转移反应的研究进展[J]. 有机化学, 2023, 43(3): 1036-1044.

Luomo Li, Xiaohui Yang. Recent Advances in Ionic Transfer Reactions[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1036-1044.

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图/表 21

图式1. 离子转移反应机理

Scheme 1. Mechanism of ionic transfer reaction

图式2. N-硅基取代二氢吡啶的脱硅烷反应

Scheme 2. Elimination of the silane from the N-silyl-dihydro- pyridine

图式3. B(C6F5)3催化原位生成硅烷反应机理

Scheme 3. Reaction mechanism of B(C6F5)3-catalyzed in situ silane generation

图式4. B(C6F5)3催化烯烃的转移氢硅化反应

Scheme 4. B(C6F5)3-catalyzed transfer hydrosilylation of alkenes

图式5. 使用甲硅烷等价物的烯烃转移氢硅化反应

Scheme 5. Transfer hydrosilylation of alkenes utilizing the SiH4-surrogates

图式6. 氨基亚甲基的负氢离子攫取

Scheme 6. Hydride abstraction from amino methylene

图式7. 二异丙基胺作为氢供体的转移氢化反应

Scheme 7. Transfer hydrogenation utilizing diisopropylamine as the hydrogen donor

图式8. 使用1,4-环己二烯类氢供体的亚胺转移氢化反应

Scheme 8. Transfer hydrogenation of imines utilizing 1,4-cyclo- hexadiene-type hydrogen donor

图式9. 使用1,4-环己二烯类氢供体的烯烃转移氢化反应

Scheme 9. Transfer hydrogenation of alkenes utilizing 1,4- cyclohexadiene-type hydrogen donor

图式10. Br?nsted酸催化烯烃和亚胺的转移氢化反应

Scheme 10. Br?nsted acid-catalyzed transfer hydrogenation of alkenes and imines

图式11. 三溴化铟催化2-炔基烯酮的还原环化反应

Scheme 11. InBr3-catalyzed reductive cyclization of 2-alkynyl enones

图式12. 离子转移氢氘化反应的区域选择性

Scheme 12. Regioselectivities of ionic transfer hydrodeuteration reactions

图式13. B(C6F5)3-催化区域选择性烯烃离子转移氢氘化反应

Scheme 13. B(C6F5)3-catalyzed regioselective ionic transfer hydrodeuteration of alkenes

图式14. 三氟化硼催化区域发散性烯烃离子转移氢氘化反应

Scheme 14. BF3-catalyzed regiodivergent ionic transfer hydrodeuteration of alkenes

图式15. 三溴化铟催化烯烃的区域选择性离子转移氢氘化反应

Scheme 15. InBr3-catalyzed regiodivergent ionic transfer hydro- deuteration of alkenes

图式16. Br?nsted酸催化炔烃离子转移氢碘化反应

Scheme 16. Br?nsted acid-catalyzed ionic transfer hydroiodination of alkynes

图式17. Br?nsted酸催化炔烃离子转移氢溴化反应

Scheme 17. Br?nsted acid-catalyzed ionic transfer hydrobromination of alkynes

图式18. Br?nsted酸催化离子转移氢氯化反应

Scheme 18. Br?nsted acid-catalyzed ionic transfer hydrochlorination reaction

图式19. 离子转移氢锗化反应

Scheme 19. Ionic transfer hydrogermylation reaction

图式20. 离子转移氢氰化反应

Scheme 20. Ionic transfer hydrocyanation reaction

图21. 离子转移氢甲基烯丙基化反应

Scheme 21. Ionic transfer hydromethallylation reaction

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