基于碳氢键断裂的金属催化的内烯烃不对称氢芳基化进展

doi:10.6023/cjoc202406049

摘要/Abstract

芳基碳氢键对烯烃的不对称加成是构建苄基手性中心的有效方法, 具有原料简单易得、原子经济性高、产物结构多样等优点. 芳基碳氢键对端位烯烃的加成研究较早, 取得了较大进展. 相较而言, 芳基碳氢键对内烯烃的不对称加成研究较为滞后. 此文将简要综述金属催化的芳基碳氢键对内烯烃不对称加成的近期进展.

关键词: 碳氢键, 内烯烃, 氢芳基化, 不对称催化, 苄基手性中心

Abstract Catalytic asymmetric addition of aryl C—H bonds to alkenes is an effective method for constructing benzylic chiral centers, offering advantages such as readily available starting materials, high atom economy, and diverse product structures. The study of the addition of aryl C—H bonds to terminal alkenes began earlier and has made significant progress. In contrast, research on the asymmetric addition of aryl C—H bonds to internal alkenes has been relatively lagging behind. The recent advances in metal-catalyzed asymmetric addition of aryl C—H bonds to internal alkenes are reviewed.

Key words: C—H bond, internal alkene, hydroarylation, asymmetric catalysis, benzylic chiral center

引用此文

林恩泽, 李必杰. 基于碳氢键断裂的金属催化的内烯烃不对称氢芳基化进展[J]. 有机化学, 2025, 45(2): 546-558.

Enze Lin, Bijie Li. Recent Progress in Metal-Catalyzed Asymmetric Hydroarylation of Internal Alkenes Through C—H Cleavage[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 546-558.

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图/表 15

图式1. 早期Murai类型的反应

Scheme 1. Early Murai type reactions

图式2. 张力烯烃氢芳基化的早期探索

Scheme 2. Early exploration of asymmetric hydroarylation of strained olefins

图式3. 铱催化的张力烯烃的不对称氢芳基化反应

Scheme 3. Asymmetric hydroarylation reaction of strained olefins catalyzed by iridium

图式4. 构建多样手性中心的张力烯烃的不对称氢芳基化反应

Scheme 4. Asymmetric hydroarylation reaction of strained olefins with diverse arenes

图式5. 铱催化的杂环化合物对张力烯烃的不对称加成反应

Scheme 5. Iridium catalyzed asymmetric addition reaction of heterocyclic compounds to strained olefins

图式6. 镍催化的张力烯烃的不对称氢芳基化反应

Scheme 6. Asymmetric hydroarylation reaction of strained olefins catalyzed by nickel

图式7. 铱催化的烯基醚的不对称氢芳基化反应

Scheme 7. Asymmetric hydroarylation of alkenyl ethers catalyzed by iridium

图式8. 构建多样手性中心的烯基醚的不对称氢芳基化反应

Scheme 8. Asymmetric hydroarylation reaction of alkenyl ethers with diverse arenes

图式9. 铱催化的杂环化合物对烯基酰胺的不对称加成反应

Scheme 9. Iridium catalyzed asymmetric addition reaction of heterocyclic compounds to enamides

图式10. 铱催化的α,β-不饱和羰基化合物的不对称氢芳基化反应

Scheme 10. Asymmetric hydroarylation of α,β-unsaturated carbonyl compounds catalyzed by iridium

图式11. 通过抗衡阴离子策略实现α,β-不饱和羰基化合物的不对称氢芳基化反应

Scheme 11. Asymmetric hydroarylation of α,β-unsaturated carbonyl compounds through counter-anion strategy

图式12. 钴催化的马来酰亚胺的不对称氢芳基化反应

Scheme 12. Asymmetric hydroarylation of maleimide catalyzed by cobalt

图式13. 铑催化的马来酰亚胺的不对称氢芳基化反应

Scheme 13. Asymmetric hydroarylation of maleimide catalyzed by rhodium

图式14. 铑催化的硝基烯烃的不对称氢芳基化反应

Scheme 14. Asymmetric hydroarylation of nitroalkenes catalyzed by rhodium

图式15. 镍催化的苯乙烯类的不对称氢芳基化反应

Scheme 15. Asymmetric hydroarylation of styrene catalyzed by nickel

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