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A Copper‐Catalyzed Aerobic [1,3]‐Nitrogen Shift through Nitrogen‐Radical 4‐ exo ‐trig Cyclization
Author(s) -
Li Yan,
Wang Rui,
Wang Tao,
Cheng XiuFen,
Zhou Xin,
Fei Fan,
Wang XiSheng
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201709894
Subject(s) - chemistry , catalysis , benzylamine , copper , catalytic cycle , nitrogen , ring (chemistry) , radical , oxygen , indole test , radical cyclization , inert gas , photochemistry , inert , medicinal chemistry , organic chemistry
A novel radical [1,3]‐nitrogen shift catalyzed by copper diacetate under an oxygen atmosphere (1 atm) has been developed for the construction of a diverse range of indole derivatives from α,α‐disubstituted benzylamine. In this reaction, oxygen was used as a clean terminal oxidant, and water was produced as the only by‐product. Five inert bonds were cleaved, and two C−N bonds and one C−C double bond were constructed in one pot during this transformation. This unique method demonstrated broad application protential for the late‐stage modification of biologically active natural products and drugs. Mechanistic investigations indicate that a unique 4‐ exo ‐trig cyclization of an aminyl radical onto a phenyl ring is involved in the catalytic cycle.