可见光光氧化还原催化的三级胺α位C-H氰基化反应

doi:10.6023/A16080414

化学学报 ›› 2017, Vol. 75 ›› Issue (1): 110-114.DOI: 10.6023/A16080414 上一篇下一篇

所属专题：有机光化学

研究论文

可见光光氧化还原催化的三级胺α位C-H氰基化反应

周泉泉, 刘丹, 肖文精, 陆良秋

农药与化学生物学教育部重点实验室和化学学院华中师范大学武汉 430079

投稿日期:2016-08-15 修回日期:2016-10-07 发布日期:2016-10-10
通讯作者: 陆良秋,E-mail:luliangqiu@mail.ccnu.edu.cn;Tel.:027-67862041;Fax:027-67862041 E-mail:luliangqiu@mail.ccnu.edu.cn
基金资助:
项目受国家自然科学基金（Nos.21232003，21472057和21572074）资助.

Visible-Light Photoredox Catalytic α-Cyanation Reactions of Tertiary Amines

Zhou Quanquan, Liu Dan, Xiao Wenjing, Lu Liangqiu

Key Laboratory of Pesticide & Chemical Biology Ministry of Education and College of Chemistry, Central China Normal University, Wuhan 430079

Received:2016-08-15 Revised:2016-10-07 Published:2016-10-10
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21232003, 21472057 and 21572074).

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1. 可见光光氧化还原催化的三级胺α位C-H氰基化反应.PDF(2567KB)

摘要/Abstract

报道了可见光光氧化还原催化的三级胺α-位碳-氢键的氰基化反应.该反应使用高价碘氰基试剂作为安全的氰基源，避免生成剧毒的氰基负离子、无需使用额外的氧化剂，具有反应条件温和、官能团兼容性好、操作简便安全等优点.此外，通过应用可见光光氧化还原催化策略，首次实现了可见光催化的烷基羧酸在温和条件下的脱羧氰基化反应.这些反应为α-氨基腈类化合物和烷基腈类化合物的合成提供了一种有效的方法.

关键词: 可见光光氧化还原催化, 氰基化, α-氨基腈, 三级胺, 脱羧转化

Visible-light photoredox catalysis, a novel and green catalytic strategy, has recently received increasing attention from chemists and been widely applied to organic synthesis in the past years. This catalytic strategy enables the generation of various reactive species under mild conditions without stoichiometric activation reagents and shows its significance for sustainable chemistry. α-Amino nitriles are highly versatile intermediates having extensive applications in organic synthesis and biological transformation. The oxidation of tertiary amines using stoichiometric oxidants followed by the nucleophilic addition reaction of the iminium intermediate by cyanide ion (CN^-) represents a direct approach for their synthesis. However, the use of stoichiometric oxidants and the production of huge amounts of hazardous waste (i.e., CN^-) is undesirable from environmental viewpoints. Here, we report a photoredox catalytic α-cyanation reaction of tertiary amines using cyanobenziodoxol as a stable and safe cyanide source. This protocol is favored for mild conditions, the avoidance of extra oxidant and highly toxic cyano anion, good functional tolerance as well as safe and simple operations. By doing so, a variety of α-amino nitriles are afforded in good to excellent yields. A sunlight-driven reaction and a gram-scale reaction further demonstrate the utility of this methodology. In addition, we also succeed to apply the same strategy to the decarboxylative cyanation of carboxylic acids, affording the nitriles in moderate yields. A possible mechanism was proposed on the basis of known literature and our previous reports. The representative procedure for the α-cyanation reaction of tertiary amines is as following:N-phenyl piperidine 1a (0.48 mmol), cyanobenziodoxol 2a (0.40 mmol), photocatalyst Ir[dF(CF₃)PPy]₂(dtbbpy)PF₆ (0.008 mmol) and CsHCO₃ (0.60 mmol) were dissolved in DCM (8 mL). Then, the resulting mixture was degassed via 'freeze-pump-thaw' procedure (3 times). After that, the solution was stirred at a distance of ca. 5 cm from a 7 W blue LEDs (450~460 nm) at room temperature for 16 h. Upon completion, the crude product was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate 30:1~10:1) directly to give the desired product. The procedure for the decarboxylative cyanation of carboxylic acids is similar.

Key words: visible-light photoredox catalysis, cyanation, α-amino nitrile, tertiary amine, decarboxylative transformation

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周泉泉, 刘丹, 肖文精, 陆良秋. 可见光光氧化还原催化的三级胺α位C-H氰基化反应[J]. 化学学报, 2017, 75(1): 110-114.

Zhou Quanquan, Liu Dan, Xiao Wenjing, Lu Liangqiu. Visible-Light Photoredox Catalytic α-Cyanation Reactions of Tertiary Amines[J]. Acta Chim. Sinica, 2017, 75(1): 110-114.

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可见光光氧化还原催化的三级胺α位C-H氰基化反应

Visible-Light Photoredox Catalytic α-Cyanation Reactions of Tertiary Amines

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