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Regiodivergent and Diastereoselective CuH‐Catalyzed Allylation of Imines with Terminal Allenes
Author(s) -
Liu Richard Y.,
Yang Yang,
Buchwald Stephen L.
Publication year - 2016
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.201608446
Subject(s) - allene , imine , chemistry , nucleophile , functional group , density functional theory , catalysis , stereochemistry , combinatorial chemistry , computational chemistry , organic chemistry , polymer
A copper‐catalyzed, chemoselective hydrometalation process enables the use of simple allenes as allylmetal nucleophile surrogates in imine allylation reactions. By modulating the nitrogen‐protecting group, either highly branched‐ or linear‐selective addition can be achieved from the same allene. Both reactions exhibit excellent diastereoselectivity and broad functional‐group tolerance. Preliminary results indicate that good enantioselectivity can also be achieved in the linear‐selective reaction. Finally, a mechanistic model for the regiodivergence is proposed on the basis of density functional theory calculations.