光氧化还原镍催化羧酸脱氧偶联的研究进展

doi:10.6023/cjoc202603006

摘要/Abstract

光氧化还原/镍双催化体系已成为一种温和且高效的平台, 可用于羧酸的直接脱氧偶联反应. 该策略充分利用羧酸本身储量丰富、结构多样的特点, 来构建高价值的酮骨架结构. 根据羧酸的原位活化方式, 包括使用二碳酸二甲酯(DMDC)、二碳酸二叔丁酯(Boc₂O)和三苯基膦(PPh₃), 对近期研究进展进行了分类总结, 并探讨了在底物范围、反应设计及机理认识等方面取得的进展. 这些突破性成果凸显了该双催化平台独特的反应活性, 并为可持续合成领域的未来发展指明了方向.

关键词: 光氧化还原, 镍催化, 脱氧, 羧酸

Photoredox/nickel dual catalysis has emerged as a mild and efficient platform for the direct deoxygenative coupling of carboxylic acids, capitalizing on their inherent abundance and structural diversity to assemble high-value ketone scaffolds. This review summarizes recent advances categorized by the in situ activation of carboxylic acids, including dimethyl dicarbonate, di-tert-butyl dicarbonate (Boc₂O), and triphenylphosphine (PPh₃), with discussion on progress in substrate scope, reaction design, and mechanistic understanding. These advances highlight the unique reactivity of this dual catalysis platform and point toward future opportunities in sustainable synthesis.

Key words: photoredox, nickel catalysis, deoxygenation, carboxylic acids

引用此文

王东平, 张淯新, 魏闪闪, 王峰娇, 朱丛军. 光氧化还原镍催化羧酸脱氧偶联的研究进展[J]. 有机化学, 2026, 46(7): 2669-2682.

Dongping Wang, Yuxin Zhang, Shanshan Wei, Fengjiao Wang, Congjun Zhu. Recent Advances in Photoredox Nickel-Catalyzed Deoxygenative Coupling of Carboxylic Acids[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2669-2682.

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图/表 16

Scheme 1. Ketone scaffolds in bioactive molecules and photoredox nickel-catalyzed deoxygenative coupling of carboxylic acids

Scheme 2. Photoredox/nickel catalysis for the direct synthesis of alkyl ketones

Scheme 3. Photoredox/nickel dual catalysis for the synthesis of C-acyl glycosides

Scheme 4. Photoredox/nickel-catalyzed synthesis of C-acyl furanosides

Scheme 5. Enantioselective C(sp3)—H acylation enables direct access to α-amino ketones

Scheme 6. Dual photoredox/nickel-catalyzed asymmetric acylation of benzylic C(sp3)—H bonds

Scheme 7. Enantioselective C—H acylation of saturated N-heterocycles

Scheme 8. Direct allylic C(sp3)—H acylation of alkenes

Scheme 9. Selective cross-ketonization of carboxylic acids

Scheme 10. Direct deoxygenative cross-coupling of carboxylic acids and alcohols

Scheme 11. Aromatization-driven acylation of spiro-dihydroquinazolones

Scheme 12. Direct ketone synthesis from carboxylic acids and organohalides

Scheme 13. Photoredox/nickel-catalyzed hydroacylation of ethylene

Scheme 14. Deoxygenative alkenylation of carboxylic acids for tetrasubstituted alkene synthesis

Scheme 15. Nickel-catalyzed radical thioesterification via sensitized electron transfer

Scheme 16. Highly selective radical C—C coupling of carboxylic acids

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