铜催化烯丙位C-H键不对称氧化反应

doi:10.6023/cjoc202605030

研究论文

铜催化烯丙位C-H键不对称氧化反应

李家圆^a, 陈品红^a, 刘国生^*,a

^a 新基石科学实验室中国科学院中国科学院大学上海有机化学研究所金属有机化学全国重点实验室沪港化学合成联合实验室上海 200032

收稿日期:2026-05-30 修回日期:2026-07-13
基金资助:
国家重点研发计划 (No. 2021YFA1500100), 中国科学院战略性先导科技专项 (No. XDB0610000), 国家自然科学基金 (Nos. 22331012, 22561160127, and 92256301), 上海市基础研究先行区计划, 新基石科学基金会资助项目.

Copper-Catalyzed Enantioselective Oxidation of Allylic C-H Bonds

Li Jiayuan^a, Chen Pinhong^a, Liu Guosheng^a,*

^aNew Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Received:2026-05-30 Revised:2026-07-13
Contact: ^*E-mail: gliu@mail.sioc.ac.cn
Supported by:
National Key R&D Program of China (No. 2021YFA1500100), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB0610000), the National Nature Science Foundation of China (Nos. 22331012, 22561160127, and 92256301), and Shanghai Pilot Program for Basic Research. G.L. acknowledges support from the New Cornerstone Science Foundation.

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摘要/Abstract

烯丙位C-H键的不对称氧化是构建手性烯丙醇及其衍生物的重要策略, 但由于C-H键惰性高及立体选择性控制困难, 该转化极具挑战性. 本文发展了一种铜催化芳基烯烃烯丙位C-H键的不对称氧化反应, 实现了以简单烯烃为当量原料直接构建手性烯丙酯的方法. 该反应条件温和,具有良好的官能团兼容性与底物普适性, 能够以中等至良好的收率及良好到优秀的对映选择性获得手性烯丙酯产物.

关键词: 烯丙位C-H键氧化, 不对称催化, 铜催化, 氢原子转移, 手性烯丙酯

Enantioselective allylic C-H oxidation represents an attractive strategy for the synthesis of chiral allylic oxygenated compounds. However, the development of catalytic asymmetric variants remains challenging due to the inherent inertness of C-H bonds and the difficulty in controlling stereoselectivity during C-H functionalization. Herein, we report a copper-catalyzed enantioselective allylic C-H oxidation that enables the direct synthesis of chiral allylic esters from simple alkenes. The reaction employs a chiral ligand-supported copper catalyst in combination with an N-Cl reagent to generate an N-centered radical capable of selective hydrogen atom transfer (HAT) to the allylic position of alkenes, forming an allylic radical intermediate. Subsequent capture of this radical by a copper-carboxylate species enables enantioselective C-O bond formation, affording the desired chiral allylic esters. The transformation proceeds under mild conditions and exhibits a broad substrate scope, accommodating both cyclic and acyclic alkenes with moderate to good yields and high levels of enantioselectivity. Notably, the reaction can be conducted with the alkene as the limiting reagent, addressing a common limitation of traditional allylic oxidation methods.

Key words: allylic C-H oxidation, asymmetric catalysis, copper catalysis, hydrogen atom transfer (HAT), chiral allylic ester

引用此文

李家圆, 陈品红, 刘国生. 铜催化烯丙位C-H键不对称氧化反应[J]. 有机化学, doi: 10.6023/cjoc202605030.

Li Jiayuan, Chen Pinhong, Liu Guosheng. Copper-Catalyzed Enantioselective Oxidation of Allylic C-H Bonds[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202605030.

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