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Synergistic catalysis for cascade allylation and 2-aza-cope rearrangement of azomethine ylides.

ABSTRACT: The efficient construction of enantiomerically enriched molecules from simple starting materials via catalytic asymmetric synthesis strategies is a key challenge in synthetic chemistry. Metallated azomethine ylides are commonly-used synthons for the preparation of N-heterocycles and α-amino acids. Remarkably, to date, the utilization of azomethine ylides for the facile access to chiral amines has proven elusive. Here, we report that a synergistic Cu/Ir-catalytic system combined with careful tuning of the steric congestion can be used to convert aldimine esters to a variety of chiral homoallylic amines via a cascade allylation/2-aza-Cope rearrangement. The elucidation of the distinct effects of each stereogenic center of the allylation intermediates on the stereochemical outcome and chirality transfer in the rearrangement further guided the selection of catalysts combination.

SUBMITTER: Wei L

PROVIDER: S-EPMC6453969 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Synergistic catalysis for cascade allylation and 2-aza-cope rearrangement of azomethine ylides.

Wei Liang L Zhu Qiao Q Xiao Lu L Tao Hai-Yan HY Wang Chun-Jiang CJ

Nature communications 20190408 1

The efficient construction of enantiomerically enriched molecules from simple starting materials via catalytic asymmetric synthesis strategies is a key challenge in synthetic chemistry. Metallated azomethine ylides are commonly-used synthons for the preparation of N-heterocycles and α-amino acids. Remarkably, to date, the utilization of azomethine ylides for the facile access to chiral amines has proven elusive. Here, we report that a synergistic Cu/Ir-catalytic system combined with careful tuni ...[more]

PMID: 30962429

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