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Asymmetric Cycloisomerization of o ‐Alkenyl‐ N ‐Methylanilines to Indolines by Iridium‐Catalyzed C(sp 3 )−H Addition to Carbon–Carbon Double Bonds
Author(s) -
Torigoe Takeru,
Ohmura Toshimichi,
Suginome Michinori
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.201708578
Subject(s) - cycloisomerization , iridium , stereocenter , intramolecular force , enantioselective synthesis , chemistry , catalysis , stereochemistry , double bond , medicinal chemistry , triple bond , organic chemistry
Highly enantioselective cycloisomerization of N ‐methylanilines, bearing o ‐alkenyl groups, into indolines is established. An iridium catalyst bearing a bidentate chiral diphosphine effectively promotes the intramolecular addition of the C(sp 3 )−H bond across a carbon–carbon double bond in a highly enantioselective fashion. The reaction gives indolines bearing a quaternary stereogenic carbon center at the 3‐position. The reaction mechanism involves rate‐determining oxidative addition of the N ‐methyl C−H bond, followed by intramolecular carboiridation and subsequent reductive elimination.