中文摘要：

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.

英文摘要：

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[d F（CF3）PPy]2（dtbbpy）PF6（0.008 mmol） and Cs HCO3（0.60 mmol） were dissolved in DCM（8 m L）. Then, the resulting mixture was degassed via ‘freeze-pump-thaw＇ procedure（3 times）. After that,