3 years ago

A Copper-Catalyzed Aerobic [1,3]-Nitrogen Shift through Nitrogen-Radical 4-exo-trig Cyclization

A Copper-Catalyzed Aerobic [1,3]-Nitrogen Shift through Nitrogen-Radical 4-exo-trig Cyclization
Xiu-Fen Cheng, Xin Zhou, Fan Fei, Tao Wang, Xi-Sheng Wang, Rui Wang, Yan Li
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. Find your places, please! Oxygen was used as a clean terminal oxidant and water was produced as the only by-product in a radical [1,3]-nitrogen shift catalyzed by copper diacetate for the construction of indoles from α,α-disubstituted benzyl amines (see scheme). In this transformation suitable for the late-stage modification of biologically active molecules, five inert bonds were cleaved, and two C−N bonds and one C−C double bond were formed.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201709894

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