不对称催化质子化构建α-叔碳羰基化合物研究进展

doi:10.6023/cjoc202211045

摘要/Abstract

不对称催化质子化反应是构建含有α-叔碳立体中心手性羰基化合物最直接、有效的方法, 被广泛用于有机合成和药物化学中. 近几十年, 该领域发展迅速, 基于底物种类、催化体系和反应类型的相关综述相继被报道. 更新并总结了该领域2019年以来的重要进展, 主要通过烯醇或其衍生物为底物的直接不对称质子化和原位生成烯醇化物/α-碳负离子或自由基的不对称串联质子化这两种反应方式介绍相关工作, 以底物种类为主线, 穿插不同催化体系、活化模式以及催化策略和手段. 期望通过这些研究为化学研究者们提供思路, 进一步促进羰基化学和不对称催化等领域的发展, 为天然产物及其中间体、药物、候选药物等具有高附加值手性分子的简单、高效合成提供助力.

关键词: 不对称催化, 质子化, 手性羰基化合物, α-叔碳立体中心, 烯醇化物, 小分子催化, 路易斯酸催化

Catalytic enantioselective protonation (EP) is a straightforward and effective approach to construct enantioenriched carbonyl compounds containing a tertiary stereocenter at its α-position, which has been widely applied in organic synthesis and medicinal chemistry. This field has significant advances in recent decades, and relevant reviews based on substrate category, catalytic system and reaction type have been reported successively. In this paper, new developments in this field are updated and summarized since 2019, which are classied into the directly catalytic asymmetric protonation of performed enolates and the enantioselective protonation of in situ enolates, α-carbanion, or α-radical intermediates, involving a variety of substrate categories, catalytic systems, activation modes, as well as catalytic strategies and means. It is expected that these studies can inspire chemists to continuously contribute to this field and further promote the development of carbonyl chemistry, asymmetric catalysis and other related fields, and provide facile and efficient access to high-value chiral molecules, including natural products and their intermediates, drugs, drug candidates and so on.

Key words: asymmetric catalysis, protonation, chiral carbonyl compound, α-tertiary stereocenter, enolate, organocatalysis, Lewis acid catalysis

引用此文

曹伟地, 刘小华. 不对称催化质子化构建α-叔碳羰基化合物研究进展[J]. 有机化学, 2023, 43(3): 961-973.

Weidi Cao, Xiaohua Liu. Recent Advances on Catalytic Enantioselective Protonation for Construction of α-Tertiary Carbonyl Compounds[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 961-973.

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图/表 23

图式1. 不对称质子化反应的两种类型

Scheme 1. Two categories of enantioselective protonation

图式2. 单氟取代烯醇硅醚的不对称质子化反应

Scheme 2. Enantioselective protonation of monofluorinated silyl enol ethers

图式3. 烯醇锂盐的不对称质子化反应

Scheme 3. Enantioselective protonation of lithium enolate

图式4. 烯醇酯的不对称质子化反应

Scheme 4. Enantioselective protonation of enol esters

图式5. 二硅基酮乙酰酯的不对称质子化反应

Scheme 5. Enantioselective protonation of bis-silyl ketene acetal

图式6. 米氏酸衍生物的不对称质子化反应

Scheme 6. Enantioselective protonation of Meldrum’s acid derivatives

图式7. α-重氮羰基化合物的分子内环化/不对称质子化/亲核加成串联反应

Scheme 7. Enantioselective intramolecular cyclization/protonation/nucleophilic addition cascade reaction of α-diazo carbonyl compounds

图式8. 联烯酮与吡咯的不对称质子化反应

Scheme 8. Enantioselective protonation of ketenes with pyrroles

图式9. 活化醛在水相中的不对称质子化反应

Scheme 9. Enantioselective protonation of activated aldehydes in water

图式10. 环状端烯酮的共轭加成/不对称质子化反应

Scheme 10. Conjugate addition/enantioselective protonation of exocyclic enones

图式11. α-芳基丙烯酸的共轭加成/不对称质子化反应

Scheme 11. Conjugate addition/enantioselective protonation of α-aryl acroleic acid

图式12. α-氨基丙烯酸酯的共轭加成/不对称质子化反应

Scheme 12. Conjugate addition/enantioselective protonation of α-aminoacrylate

图式13. α-氨烷基丙烯酸酯的共轭加成/不对称质子化反应

Scheme 13. Conjugate addition/enantioselective protonation of α-aminoalkyl acrylates

图式14. β-酮酸的脱羰/不对称质子化串联反应

Scheme 14. Enantioselective decarboxylative protonation of β-ketocarboxylic acid

图式15. β-二酮的不对称逆Claisen反应/质子化反应

Scheme 15. Enantioselective retro-Claisen reaction/protonation of β-diketones

图式16. 光/小分子协同催化端烯酮的共轭加成/不对称质子化

Scheme 16. Conjugate addition/enantioselective protonation of enones by merging photocatalysis and organocatalysis

图式17. 光/Lewis酸协同催化α,β-不饱和羰基化合物的不对称自由基氢酰化反应

Scheme 17. Enantioselective radical hydroacylation of α,β-unsaturated carbonyls by merging photocatalysis and Lewis acid catalysis

图式18. 不对称Norrish-II型环化反应

Scheme 18. Asymmetric Norrish-type II cyclization

图式19. 光催化外消旋α,α-二卤代酮不对称脱卤/质子化反应

Scheme 19. Photo-catalyzed enantioselective dehalogenative protonation of racemic α,α-dihalogeno ketones

图式20. 烯烃的不对称还原交叉偶联/质子化反应

Scheme 20. Enantioselective reductive cross coupling/proto- nation of olefins

图式21. 外消旋醛的去消旋化

Scheme 21. Deracemization of racemic aldehydes

图式22. 外消旋α-氨基酸酯及类似物的去消旋化

Scheme 22. Deracemization of racemic α-amino esters and analogues

图式23. 电/小分子协同催化外消旋α-氟代酮的去三氟乙酰化/不对称质子化反应

Scheme 23. Enantioselective detrifluoroacetylative protonation of racemic α-fluoroketone by merging electrocatalysis and organocatalysis

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