可见光促进惰性碳-氢键对羰基的加成反应进展

doi:10.6023/cjoc202306011

摘要/Abstract

仲醇和叔醇是重要的有机化合物, 其结构普遍存在于具有生物活性的天然产物和药物分子中, 且可以作为上游原料制备多种高附加值化学品. 在众多合成方法中, 醛酮的亲核加成反应是合成此类化合物最有效的方法之一, 但通常需要使用预官能化底物, 不仅效率较低, 且原子经济性不高. 可见光催化的兴起, 为惰性碳-氢键的活化提供了一种温和高效的方法, 促进了惰性碳-氢键直接对醛酮加成反应的发展, 推动仲醇和叔醇的合成进入新的阶段. 根据反应机理的不同, 分别对经由还原性自由基-极性交叉、自由基-自由基交叉偶联和自由基加成机制的三类可见光诱导的惰性碳-氢键对羰基的加成反应进行了综述, 并对该领域的局限性和未来发展方向做出了简要分析.

关键词: 仲醇, 叔醇, 可见光催化, 还原性自由基-极性交叉, 自由基-自由基交叉偶联, 自由基加成

Secondary and tertiary alcohols are important structural motifs that often exist in a large number of bioactive natural products and pharmaceuticals. Moreover, they can also be used as upstream raw material for preparation of various highly valuable chemicals. Among the existing synthetic methodologies for preparation of these compounds, the nucleophilic addition of nucleophiles to aldehydes and ketones represents one of the most operative ways. However, pre-functionalized substrates are always needed for this protocol, resulting in low efficiency and poor atom economy. The growing area of photocatalysis has provided a mild and effective approach for inert C—H bond activation. As a result, the photocatalytic straight addition of inert C—H bond to carbonyls has been developed, which affords the synthesis of secondary and tertiary alcohols in a new manner. The visible-light induced addition reaction of inert C—H bond to carbonyls was classified by three different mechanisms: reductive radical-polar crossover (RRPCO), radical-radical cross coupling as well as radical addition, and reviewed, respectively. Finally, the limitations and future developments of this research field are discussed.

Key words: secondary alcohol, tertiary alcohol, visible-light catalysis, reductive radical-polar crossover, radical-radical cross coupling, radical addition

引用此文

童红恩, 郭宏宇, 周荣. 可见光促进惰性碳-氢键对羰基的加成反应进展[J]. 有机化学, 2024, 44(1): 54-69.

Hong'en Tong, Hongyu Guo, Rong Zhou. Progress on Visible-Light Promoted Addition Reactions of Inert C—H Bonds to Carbonyls[J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 54-69.

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图/表 27

图式1. 可见光促进碳氢键对羰基加成的可能机理

Scheme 1. Plausible mechanisms for the visible-light promoted addition of C—H bond into carbonyls

图式2. 可见光与铬协同催化醛的烯丙基化反应

Scheme 2. Allylation of aldehydes enabled by synergistic visible-light and chromium catalysis

图式3. 可见光与铬协同催化醛的不对称烯丙基化反应

Scheme 3. Asymmetrical allylation of aldehydes enabled by synergistic visible-light and chromium catalysis

图式4. 可见光催化惰性烯烃参与的醛的烯丙基化反应

Scheme 4. Visible-light catalyzed allylation of aldehydes involving unactivated alkenes

图式5. 十聚钨酸盐催化醛的烷基化反应

Scheme 5. Decatungstate-catalyzed alkylation of aldehydes

图式6. 烷基化反应的可能机理

Scheme 6. Proposed mechanism for the alkylation of aldehydes

图式7. 光氧化还原催化醛的烯丙基化反应合成单保护1,2-二醇

Scheme 7. Synthesis of monoprotected 1,2-diols via photoredox catalytic allylation of aldehydes

图式8. 可见光促进铜\铬协同催化芳香醛的烷基化反应

Scheme 8. Visible-light promoted alkylation of aromatic aldehydes via synergistic copper/chromium catalysis

图式9. 可见光催化无金属参与的醛酮苄基化反应

Scheme 9. Visible-light catalyzed metal-free benzylation of aldehydes and ketones

图式10. 有机小分子与可见光协同催化环酮的β位C—H官能化反应

Scheme 10. β-C—H functionalization of cyclic ketones via merger of photoredox and organocatalysis

图式11. 可见光促进铑催化2-酰基咪唑和2-酰基吡啶的β位不对称C—H官能化反应

Scheme 11. Visible-light promoted rhodium-catalyzed asymmetrical β-C—H functionalization of 2-acyl imidazoles and 2-acylpyridines

图式12. 可见光促进铱催化三氟甲基酮的不对称胺烷基化反应

Scheme 12. Visible-light promoted iridium-catalyzed asymmetrical aminoalkylation of trifluoromethyl ketones

图式13. 可见光催化芳香醛的胺烷基化反应

Scheme 13. Visible-light catalyzed aminoalkylation of aromatic aldehydes

图式14. 可见光催化芳香醛酮的胺烷基化反应

Scheme 14. Visible-light catalyzed aminoalkylation of aromatic aldehydes and ketones

图式15. 可见光催化酮的分子内胺烷基化反应

Scheme 15. Visible-light catalyzed intramolecular aminoalkylation of ketones

图式16. 可见光催化经由质子偶合电子转移过程的芳香醛酮的胺烷基化反应

Scheme 16. Aminoalkylation of aromatic aldehydes and ketones by photocatalytic proton-coupled electron transfer

图式17. 可见光催化靛红衍生物的胺烷基化反应

Scheme 17. Visible-light catalyzed aminoalkylation of isatin derivatives

图式18. 可见光诱导靛红衍生物的硫烷基化反应

Scheme 18. Visible-light promoted sulfur alkylation of isatin derivatives

图式19. 靛红衍生物硫烷基化反应的可能机理

Scheme 19. Proposed mechanism for sulfur alkylation of isatin derivatives

图式20. 可见光诱导靛红衍生物的苄基化反应

Scheme 20. Visible-light promoted benzylation of isatin derivatives

图21. 可见光促进9-芴酮衍生物的苄基化反应

Scheme 21. Visible-light promoted benzylation of 9-fluorenones

图22. 可见光与硫醇协同催化酮羰基的烯丙基化反应

Scheme 22. Allylation of ketones enabled by synergistic visible-light and thiol catalysis

图式23. 溴负离子作为HAT试剂的酮苄基化反应和半导体作为光敏剂的酮烯丙基化反应

Scheme 23. Benzylation of ketones with Br－ as HAT reagent and allylation of ketones with semiconductor as photosensitizer

图式24. 可见光催化α-酮酯的烯丙基化反应

Scheme 24. Visible-light catalyzed allylation of α-ketoesters

图式25. 可见光催化α-酮酯的芳基化反应

Scheme 25. Visible-light catalyzed arylation of α-ketoesters

图26. 可见光催化2-酰基吡啶的不对称烷基化反应

Scheme 26. Visible-light catalyzed asymmetric alkylation of 2-acyl pyridines

图27. 可见光、TPI与钛(III)协同催化的醛酮烷基化反应

Scheme 27. Alkylation of ketones and aldehydes under synergistic visible-light, TPI and titanium(III) catalysis

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