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Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.

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.

SUBMITTER: Liu RY

PROVIDER: S-EPMC5198719 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.

Liu Richard Y RY Yang Yang Y Buchwald Stephen L SL

Angewandte Chemie (International ed. in English) 20161010 45

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 ...[more]

PMID: 27723269

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