可见光催化烯烃的氢胺化和氢(磺)酰胺化反应

doi:10.6023/cjoc202511015

有机化学 ›› 2026, Vol. 46 ›› Issue (4): 1166-1180.DOI: 10.6023/cjoc202511015 上一篇下一篇

综述与进展

可见光催化烯烃的氢胺化和氢(磺)酰胺化反应

张皓然^a^,^b, 贾均松^a, 俞琼^b, 吴宇^a, 李玉龙^a^,^*(), 舒伟^b^,^*()

^a 四川轻化工大学化学与环境工程学院绿色催化四川省高校重点实验室绿色催化四川省高校重点实验室四川自贡 643000
^b 南方科技大学深圳市格拉布斯研究院化学系广东省催化重点实验室广东深圳 518055

收稿日期:2025-11-24 修回日期:2026-01-02 发布日期:2026-02-06
通讯作者: 李玉龙, 舒伟
基金资助:
国家自然科学基金(22371115); 国家自然科学基金(22171127); 国家自然科学基金(22373056); 国家自然科学基金(22501125); 国家自然科学基金(22501190); 四川省自然科学基金(2025ZNSFSC0128)

Visible-Light-Catalyzed Hydroamination, Hydroamidation and Hydrosulfonamidation of Alkenes

Haoran Zhang^a^,^b, Junsong Jia^a, Qiong Yu^b, Yu Wu^a, Yulong Li^a^,^*(), Wei Shu^b^,^*()

^a College of Chemistry and Environmental Engineering, Key Laborotory of Green Chemistry of Sichuan Instituttes of Higher Education, SichuanUniversity of Science and Engineering, Zigong, Sichuan 643000
^b Shenzhen Grubbs Institute, Department of Chemistry, Guangdong Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055

Received:2025-11-24 Revised:2026-01-02 Published:2026-02-06
Contact: Yulong Li, Wei Shu
Supported by:
National Natural Science Foundation of China(22371115); National Natural Science Foundation of China(22171127); National Natural Science Foundation of China(22373056); National Natural Science Foundation of China(22501125); National Natural Science Foundation of China(22501190); Natural Science Foundation of Sichuan Province(2025ZNSFSC0128)

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摘要/Abstract

N-烷基胺、酰胺与磺酰胺作为重要的含氮结构单元, 广泛存在于药物分子、农用化学品以及功能材料中, 其高效、精准合成对分子设计与后期修饰具有重要意义. 在现有合成方法中, C—N键构建是获取此类化合物的关键策略之一, 但传统方法构建策略通常依赖预官能化底物、强氧化/还原或高温反应条件, 容易导致过烷基化、副反应增多、区域与化学选择性控制不佳, 以及对复杂分子骨架的兼容性有限等问题. 近年来, 可见光驱动的烯烃氢胺化/氢酰胺化/氢磺酰胺化反应通过单电子转移、质子耦合电子转移、氢原子转移等多种反应机制, 在温和条件下, 实现了将简单烯烃与多种氮源的直接偶联, 从而高效合成N-烷基胺、酰胺与磺酰胺. 该反应使用烯烃作为烷基化试剂, 表现出优异的步骤经济性和官能团兼容性. 系统综述了可见光催化烯烃氢胺化/氢酰胺化/氢磺酰胺化领域的进展与关键反应路径, 并总结了不同催化体系的选择性调控策略和适用范围, 并对该领域的后续发展进行了展望, 以期为相关合成方法的选择与应用提供理论依据和实践参考.

关键词: 烯烃, 可见光催化, 氢官能团化, 碳氮成键, 含氮化合物

N-Alkylamines, amides, and sulfonamides, a class of important nitrogen-containing structural units, are ubiquitous in pharmaceutical molecules, agrochemicals, and functional materials. To this end, the efficient and precise synthesis of such substructures is of great significance for molecular design and late-stage modification. Among various synthetic approaches, C—N bond formation represents one of the key strategies. However, traditional C—N bond formation strategies heavily rely on pre-functionalized substrates under strong oxidative/reductive conditions, or elevated reaction temperature, which often suffer from over-alkylation, competitive side reactions, poor regio- and chemoselectivity, limited compatibility with molecular complexity. Over past years, visible-light-driven hydroamination, hydroamidation, and hydrosulfonamidation of alkenes have achieved efficient synthesis of N-alkylamines, amides, and sulfonamides by direct cross-coupling of simple alkenes with various nitrogen sources under mild conditions through different reaction mechanisms such as single-electron transfer, proton-coupled electron transfer, and hydrogen atom transfer. These reactions utilize alkenes as alkylation reagents, demonstrating excellent step-economy and functional group compatibility. This review summarizes the progress and key reaction pathways in the field of visible-light-catalyzed hydroamination, hydroamidation, and hydrosulfonamidation of alkenes, with an emphasis on selectivity control and scope of different catalytic systems, and provides an outlook on future developments in this area, aiming to offer theoretical and practical guidance for further development and application to target synthesis in related areas.

Key words: alkenes, visible-light-catalysis, hydrofunctionalizations, C—N bond-formation, nitrogen-containing compounds

引用此文

张皓然, 贾均松, 俞琼, 吴宇, 李玉龙, 舒伟. 可见光催化烯烃的氢胺化和氢(磺)酰胺化反应[J]. 有机化学, 2026, 46(4): 1166-1180.

Haoran Zhang, Junsong Jia, Qiong Yu, Yu Wu, Yulong Li, Wei Shu. Visible-Light-Catalyzed Hydroamination, Hydroamidation and Hydrosulfonamidation of Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1166-1180.

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图/表 16

图式1. N-烷基胺、酰胺与磺酰胺的重要性及代表性合成方法

Scheme 1. Significance and representative strategies for the synthesis of N-alkylamines, amides, and sulfonamides

图式2. 可见光催化非活化烯烃与脂肪仲胺的分子间氢胺化反应

Scheme 2. Photocatalytic intermolecular hydroamination of unactivated alkenes with aliphatic secondary amines

图式3. 可见光催化非活化烯烃与脂肪伯胺的反马氏氢胺化反应

Scheme 3. Photocatalytic anti-Markovnikov hydroamination of unactivated alkenes with aliphatic primary amines

图式4. 有机光催化烯烃氢胺化反应直接制备伯胺

Scheme 4. Direct synthesis of primary amines from organophotocatalytic hydroamination of alkenes

图式5. 光催化(杂)芳伯胺与烯烃的反马氏氢胺化反应

Scheme 5. Photocatalytic anti-Markovnikov hydroamination of heteroaryl primary amines with alkenes

图式6. 膦-光氧化还原协同催化吡唑与烯烃的氢胺化反应

Scheme 6. Phosphine-photoredox cooperative catalytic hydroamination of azoles with alkenes

图式7. PCET驱动的光催化烯烃分子内氢酰胺化

Scheme 7. Photocatalytic intramolecular hydroamidation of alkenes enabled by PCET

图式8. 有机光催化烯烃分子内还原氢酰胺化反应

Scheme 8. Organophotocatalytic intramolecular reductive hydroamidation of alkenes

图式9. 提升光催化烯烃的氢酰胺化的量子效率的通用策略

Scheme 9. General strategy for improving the quantum efficiency of photocatalytic hydroamidation of alkenes

图式10. PCET促进的可见光催化烯烃与N-烷基酰胺的分子内氢酰胺化反应

Scheme 10. PCET-enabled visible-light-catalyzed intramolecular hydroamidation of alkenes with N-alkyl amides

图式11. 基于双组分有机光氧化还原体系催化的烯烃反马氏氢磺酰胺化反应

Scheme 11. anti-Markovnikov hydrosulfonamidation of alkenes catalyzed by a two-component organic photoredox system

图式12. 通过PCET实现未活化烯烃与磺酰胺的分子间反马氏氢磺酰胺化反应

Scheme 12. Intermolecular anti-Markovnikov hydrosulfonamidation of unactivated alkenes with sulfonamides enabled by PCET

图式13. 膦/光氧化还原催化下烯烃与一级磺酰胺的反马氏氢磺酰胺化反应

Scheme 13. Phosphine and photoredox anti-Markovnikov hydrosulfonamidation of alkenes with primary sulfonamides

图式14. 可见光催化烯烃的分子间反马氏氢磺酰化反应

Scheme 14. Visible-light-catalyzed intermolecular anti-Markovnikov hydrosulfonamidation of alkenes

图式15. 有机光催化烯烃分子内反马氏氢磺酰胺化反应

Scheme 15. Organophotocatalytic anti-Markovnikov intramolecular hydrosulfonamidation of alkenes

图式16. 可见光催化烯烃与N-磺酰基腙的分子内氢磺酰胺化反应

Scheme 16. Visible-light-catalyzed intramolecular hydrosulfonamidation of alkenes with N-tosyl hydrazones

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可见光催化烯烃的氢胺化和氢(磺)酰胺化反应

Visible-Light-Catalyzed Hydroamination, Hydroamidation and Hydrosulfonamidation of Alkenes

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参考文献 48

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