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Interweaving Visible‐Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones
Author(s) -
Tang JingJing,
Yu Xiaoqiang,
Wang Yi,
Yamamoto Yoshinori,
Bao Ming
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202016234
Subject(s) - nitrene , chemistry , photochemistry , intramolecular force , decarboxylation , intermolecular force , regioselectivity , visible spectrum , catalysis , electron transfer , substrate (aquarium) , stereochemistry , molecule , organic chemistry , materials science , oceanography , geology , optoelectronics
Herein, visible‐light‐driven iron‐catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp 3 )‐N, N=S, and N=P bond formation are described. These reactions occur with exogenous‐ligand‐free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C−H amidations strategies, an intermolecular regioselective C−H amidation via visible‐light‐induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone‐bounding iron species to quartet spin state via visible‐light irradiation.