Open AccessEnantioselective Radical Construction of 5-Membered Cyclic Sulfonamides by Metalloradical C–H Amination
Author(s) -
Yang Hu,
Kai Lang,
Chaoqun Li,
Joseph B. Gill,
Isaac Kim,
Hongjian Lü,
Kimberly B. Fields,
McKenzie K. Marshall,
Qigan Cheng,
Xin Cui,
Łukasz Wojtas,
X. Peter Zhang
Publication year - 2019
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.9b08894
Subject(s) - chemistry , amination , enantioselective synthesis , allylic rearrangement , selectivity , reactivity (psychology) , medicinal chemistry , combinatorial chemistry , catalysis , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
Both arylsulfonyl and alkylsulfonyl azides can be effectively activated by the cobalt(II) complexes of D 2 -symmetric chiral amidoporphyrins for enantioselective radical 1,5-C-H amination to stereoselectively construct 5-membered cyclic sulfonamides. In addition to C-H bonds with varied electronic properties, the Co(II)-based metalloradical system features chemoselective amination of allylic C-H bonds and is compatible with heteroaryl groups, producing functionalized 5-membered chiral cyclic sulfonamides in high yields with high enantioselectivities. The unique profile of reactivity and selectivity of the Co(II)-catalyzed C-H amination is attributed to its underlying stepwise radical mechanism, which is supported by several lines of experimental evidence.