可见光/铬协同催化的对映选择性转化反应研究进展

doi:10.6023/cjoc202512018

摘要/Abstract

光氧化还原催化与第一过渡系金属催化的协同融合, 极大推动了可持续不对称合成领域的发展. 其中, 光氧化还原催化剂与铬催化剂的结合尤为引人注目. 铬作为一种储量丰富且具有丰富单/双电子氧化还原特性的金属, 可实现新颖的反应模式与立体控制策略. 评述了近年来通过可见光/铬协同催化实现的对映选择性转化的研究进展, 分析了各组分的独特作用、协同机制及手性活化模式, 涵盖了对映选择性自由基加成、C—H键官能团化、交叉偶联及多组分反应等关键转化. 最后, 总结了这一快速发展领域当前面临的挑战与未来机遇, 并着重阐述了其在推动药物及农用化学品更可持续生产方面的巨大潜力.

关键词: 可见光, 铬, 对映选择性, 不对称, 光氧化还原, 金属光氧化还原, 自由基

The synergistic merger of photoredox catalysis with first-row transition metal catalysis has enabled a powerful development for sustainable asymmetric synthesis. Among these, the combination of photoredox catalysts with chromium complexes—an abundant metal with rich one- and two-electron redox chemistry—has unlocked novel reactivity manifolds and stereocontrol strategies. Rrecent advances in enantioselective transformations enabled by synergistic photocatalytic/chromium catalysis are examined. The unique catalyst roles, synergistic mechanisms, and activation modes are analyzed, with key transformations covered including enantioselective radical addition, C—H functionalization, cross-coupling, and multicomponent reactions. Allylic, propargylic and alkylic radical involved transformations enabled by the dual photoredox/chromium catalysis are discussed respectively. The development of this field is summarized, with emphasis on strategies aimed at expanding the substrate scope and establishing novel synthetic routes toward structurally diverse compounds. The review concludes with a highlight of current challenges and future opportunities for this rapidly developing field, emphasizing its potential for more sustainable pharmaceutical and agrochemical manufacturing.

Key words: visible light, chromium, enantioselective, asymmetry, photoredox, metallophotoredox, radical

引用此文

缪宇辰, 杞航, 黄焕明. 可见光/铬协同催化的对映选择性转化反应研究进展[J]. 有机化学, 2026, 46(4): 1481-1495.

Yu-Chen Miao, Hang Qi, Huan-Ming Huang. Recent Advances in Enantioselective Transformations Enabled by Synergistic Photoredox/Chromium Catalysis[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1481-1495.

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图/表 17

Figure 1. A typical mechanism for the enantioselective transformations enabled by synergistic photoredox/chromium catalysis

Scheme 1. Diastereoselective allylation of aldehydes by Glorius and co-workers

Scheme 2. Enantioselective allylation of aldehydes by Kanai and co-workers

Scheme 3. Allylation of aldehydes with unactivated alkenes by Kanai and co-workers

Scheme 4. Visible light-driven stereodivergent allylation of cyclic hemiacetals with butene for polypropionate synthesis by Kanai and co-workers

Scheme 5. Asymmetric addition of allylsilanes to aldehydes by Glorius and co-workers

Scheme 6. Dialkylation of 1,3-dienes by Glorius and co-workers

Scheme 7. Regio and stereoselective allylation of aldehydes via photoredox/Cr/Co triple catalysis by Wang and co-workers

Scheme 8. Enantioconvergent reductive couplings of racemic allenes and aldehydes via photoredox/Cr/Co triple catalysis by Wang and co-workers

Scheme 9. Remote alkylation of aldehydes by C—C cleavage by Huang and co-workers

Scheme 10. Enantioselective C—H functionalization of (hetero)aromatics by Huang and co-workers

Scheme 11. Three-component NHK reaction by Glorius and co-workers

Scheme 12. Chiral radical-polar crossover reaction with cyclopropanols by Huang and co-workers

Scheme 13. Stereoselective allylation of aldehydes via photoredox/Cr/Co triple catalysis by Wang and co-workers

Scheme 14. Diastereoselective allenylation of aldehyde by Wang and co-workers

Scheme 15. Photocatalyst/cobalt/chromium triple catalysis system by Tu, Zhang and co-workers

Scheme 16. Asymmetric α-C—H addition of N-sulfonyl benzylamines to aldehydes by Wang and co-workers

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