钴催化α-三氟甲基烯烃的脱氟还原偶联反应制备偕二氟烯烃

doi:10.6023/cjoc202606022

有机化学 ›› 2026, Vol. 46 ›› Issue (9): 3615-3623.DOI: 10.6023/cjoc202606022 上一篇下一篇

研究论文

钴催化α-三氟甲基烯烃的脱氟还原偶联反应制备偕二氟烯烃

任慧敏^a^,^b, 茆勇军^a^,^*(), 王子超^b^,^*(), 施世良^b^,^c^,^*()

^a 上海工程技术大学化学工程与工艺重点实验室上海 201620
^b 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032
^c 宁波中科新材料创制中心浙江宁波 315000

收稿日期:2026-06-18 修回日期:2026-07-20 发布日期:2026-08-03
基金资助:
国家自然科学基金(22325110); 国家自然科学基金(22401288); 中国科学院战略性先导科技专项(XDB0610000); 中国科学院战略性先导科技专项(XDA0540000); 上海市科学技术委员会项目(24ZR1479000); 与宁波市自然科学基金(2022J017)

Synthesis of gem-Difluoroalkenes via Cobalt-Catalyzed Defluorinative Reductive Coupling of α‑Trifluoromethyl Alkenes

Huimin Ren^a^,^b, Yongjun Mao^a^,^*(), Zichao Wang^b^,^*(), Shiliang Shi^b^,^c^,^*()

^a College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032
^c Ningbo Zhongke Creation Center of New Materials, Ningbo, Zhejiang 315000

Received:2026-06-18 Revised:2026-07-20 Published:2026-08-03
Contact:
^* E-mail: yjmao@sues.edu.cn;
wangzichao@sioc.ac.cn;
shiliangshi@sioc.ac.cn
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Natural Science Foundation of China(22325110); National Natural Science Foundation of China(22401288); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000); Strategic Priority Research Program of the Chinese Academy of Sciences(XDA0540000); Shanghai Science and Technology Committee(24ZR1479000); Ningbo Natural Science Foundation(2022J017)

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摘要/Abstract

偕二氟烯烃是一类重要的化合物, α-三氟甲基烯烃的还原烷基化反应为这类化合物的合成提供了一种直接高效的合成方法. 利用廉价金属钴作为金属催化剂, 无需额外配体即可实现α-三氟甲基烯烃的还原烷基化反应, 以良好的效率合成系列偕二氟烯烃化合物. 该反应体系具有实用高效的特点.

关键词: 偕二氟烯烃, α-三氟甲基烯烃, 钴催化, 还原烷基化反应

gem-Difluoroalkenes represent an important class of organic compounds, and the reductive alkylation of α-trifluo- romethyl alkenes serves as a straightforward and efficient synthetic strategy to access these structures. In this work, a ligand- free reductive alkylation of α-trifluoromethyl alkenes was reported using inexpensive cobalt as the catalyst, eliminating the requirement for external supporting ligands. This transformation demonstrates excellent functional group compatibility as well as good tolerance towards heterocyclic moieties, and is compatible with primary, secondary, and tertiary alkyl halide coupling partners. A diverse array of gem-difluoroalkene products was obtained in moderate to excellent yields, and gram-scale experiments further confirm the scalability of this protocol. Overall, this cobalt-catalyzed system features the advantages of practicality and high efficiency for the construction of gem-difluoroalkenes.

Key words: gem-difluoroalkenes, α‑trifluoromethyl alkenes, cobalt catalysis, reductive alkylation

引用此文

任慧敏, 茆勇军, 王子超, 施世良. 钴催化α-三氟甲基烯烃的脱氟还原偶联反应制备偕二氟烯烃[J]. 有机化学, 2026, 46(9): 3615-3623.

Huimin Ren, Yongjun Mao, Zichao Wang, Shiliang Shi. Synthesis of gem-Difluoroalkenes via Cobalt-Catalyzed Defluorinative Reductive Coupling of α‑Trifluoromethyl Alkenes[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3615-3623.

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图/表 5

图式1. (a)含偕二氟烯烃骨架的生物活性分子; (b) α-三氟甲基烯烃参与的还原烷基化反应; (c)本工作

Scheme 1. (a) Bioactive molecules containing gem-difluoro- alkene scaffolds; (b) Reductive alkylation reaction involving α-trifluoromethyl alkenes; (c) this work

表1. 反应条件的筛选和优化a

Table 1. Optimization of the reaction conditions

表2. 底物拓展

Table 2. Scope of substrates

图式2. 克级反应及控制实验

Scheme 2. Gram-scale reaction and control experiments

图式3. 可能的催化循环

Scheme 3. Possible catalytic cycle

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钴催化α-三氟甲基烯烃的脱氟还原偶联反应制备偕二氟烯烃

Synthesis of gem-Difluoroalkenes via Cobalt-Catalyzed Defluorinative Reductive Coupling of α‑Trifluoromethyl Alkenes

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