Dual Photoredox/Copper Catalysis for the Remote C(sp3)-H Functionalization of Alcohols and Alkyl Halides by N-Alkoxypyridinium Salts
Dual Photoredox/Copper Catalysis for the Remote C(sp3)-H Functionalization of Alcohols and Alkyl Halides by N-Alkoxypyridinium Salts
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DOI：
10.1002/anie.201813356
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发表时间：
2019-02-11
影响因子：
16.6
通讯作者：
Zhu, Jieping
中科院分区：
文献类型：
--
作者：
Bao, Xu;Wang, Qian;Zhu, Jieping
在温和的双光氧化还原/铜催化下，N-烷氧基吡啶鎓盐与易得的硅烷试剂（TMSN 3、TMSCN、TMSNCS）反应，高产率地得到了-叠氮基、-氰基和-硫氰基醇.该反应经历了一个多米诺骨牌过程，包括烷氧基自由基的产生，1，5-氢原子转移（1，5-HAT）和铜催化的功能化所产生的C-中心自由基。催化的对映选择性-C（sp（3））-H氰化反应的条件也被记录。
Under mild dual photoredox/copper catalysis, the reaction of N-alkoxypyridinium salts with readily available silyl reagents (TMSN3, TMSCN, TMSNCS) afforded -azido, -cyano, and -thiocyanato alcohols in high yields. The reaction went through a domino process involving alkoxy radical generation, 1,5-hydrogen atom transfer (1,5-HAT) and copper-catalyzed functionalization of the resulting C-centered radical. Conditions for catalytic enantioselective -C(sp(3))-H cyanation were also documented.