Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes
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Author(s) • • • •
Liu, Richard Y.
Yang, Yang
Buchwald, Stephen L.
Liu, Richard
Buchwald, Stephen Leffler
Date Issued
October 2016
Journal
Angewandte Chemie International Edition
Publisher
Wiley-Blackwell
Citation
Liu, Richard Y., et al. “Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.” Angewandte Chemie International Edition, vol. 55, no. 45, Nov. 2016, pp. 14077–80.
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Author's final manuscript
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1002/ANIE.201608446