Recent Advances in Enantioselective Transformations Enabled by Synergistic Photoredox/Chromium Catalysis

doi:10.6023/cjoc202512018

Abstract

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

Cite this article

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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Fig. & Tab. 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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