手性硼烷催化的对映选择性反应

doi:10.6023/cjoc202208018

摘要/Abstract

在过去的20年, 手性硼烷已发展成为一种优势催化剂并应用于不对称反应, 一系列结构丰富多样的手性骨架也被应用于手性硼烷的设计与合成中. 与手性过渡金属催化剂相比, 手性硼烷通常需要更少的催化剂用量, 更易于制备, 而且有时还能展现出更好的催化能力, 或给出与过渡金属互补的催化效果. 因此, 手性硼烷催化剂在不对称反应中具有很大的应用价值. 按照反应类型将其分为三大类, 总结和讨论手性硼烷催化的不对称反应.

关键词: 手性硼烷, 对映选择性反应, 氢化反应, 硅氢加成反应

During the past two decades, chiral boranes have emerged as one class of privileged catalysts in asymmetric reactions. A variety of chiral frameworks have been applied in the design and synthesis of chiral borane catalysts. In contrast to chiral transition metal catalysts, chiral boranes generally require lower catalyst loading and are easier to access. Sometimes they exhibit better performance than transition metal catalysts, or give complementary effects in some cases. Accordingly, this catalyst family is of great value in asymmetric reactions. The chiral borane-catalyzed enantioselective reactions are summarized and discussed, which are organized into three parts according to the reaction categories.

Key words: chiral borane, enantioselective reaction, hydrogenation, hydrosilylation

引用此文

李鑫, 宋秋玲. 手性硼烷催化的对映选择性反应[J]. 有机化学, 2022, 42(10): 3143-3151.

Xin Li, Qiuling Song. Chiral Borane-Catalyzed Enantioselective Reactions[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3143-3151.

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图/表 32

Figure 1. Representative chiral borane catalysts

Scheme 1. H2 activation by (a) transition metals and (b) frustrated Lewis pairs

Scheme 2. Enantioselective hydrogenation of imine with borane 1

Scheme 3. Enantioselective hydrogenation of imine with borane 2

Scheme 4. Enantioselective hydrogenation of imine with borane 3

Scheme 5. Enantioselective hydrogenation of imine and quinoline with boranes 4 and 5

Scheme 6. Enantioselective hydrogenation of imine and enamine with borane 6

Scheme 7. Enantioselective hydrogenation of imine with borane 7

Scheme 8. Enantioselective hydrogenation of heterocyclic compounds with borane 7

Scheme 9. Enantioselective hydrogenation of silyl enol ethers with borane 7

Scheme 10. Enantioselective hydrogenation of silyl enol ethers with borane 8

Scheme 11. Enantioselective hydrogenation of imine with borane 9

Scheme 12. Enantioselective hydrogenation of imine with boranes 10 and 11

Scheme 13. Enantioselective hydrogenation of imine with borane 12

Scheme 14. Enantioselective hydrogenation of imine with borane 13

Scheme 15. Enantioselective hydrogenation of imine with borane 14

Scheme 16. Enantioselective hydrogenation of imine with borane 15

Scheme 17. Mechanism of the chiral borane catalyzed enantioselective hydrosilylation

Scheme 18. Enantioselective hydrosilylation of imine with borane 16

Scheme 19. Enantioselective hydrosilylation of imine with borane 2

Scheme 20. Enantioselective hydrosilylation of imine with borane 7

Scheme 21. Enantioselective hydrosilylation of acetophenone with borane 17

Scheme 22. Enantioselective hydrosilylation of ketone with borane 7

Scheme 23. Enantioselective hydrosilylation of ketone with borane 18

Scheme 24. Enantioselective hydrosilylation of 1,2-dicarbonyl compound with borane 8

Scheme 25. Enantioselective hydrosilylation of chromone and flavone with borane 8

Scheme 26. Asymmetric allylstannation of aromatic aldehyde with borane 19

Scheme 27. Enantioselective transfer hydrogenation of imine with borane 7

Scheme 28. Enantioselective reduction of 2-substituted pyridine with borane 15

Scheme 29. Asymmetric vinylogous Mannich reaction of α,β- unsaturated ketone with borane 14

Scheme 30. Asymmetric electrophilic halocyclization of 2- vinylbenzyl alcohol with borane 7

Scheme 31. Hydride transfer/enantioselective [2+2] cycloaddition cascade reaction with borane 15

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