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Catalytic Asymmetric Umpolung Allylation of Imines

Jie Liu, Chao-Guo Cao, Hong-Bao Sun, Xia Zhang and Dawen Niu*

*Department of Emergency, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University, and Collaborative Innovation Center for Biotherapy, Chengdu 610041, China, Email:

J. Liu, C.-G. Cao, H.-B. Sun, X. Zhang, D. Niu, J. Am. Chem. Soc., 2016, 138, 13103-13106.

DOI: 10.1021/jacs.6b05288


An iridium-catalyzed asymmetric umpolung allylation of imines provides 1,4-disubstituted homoallylic amines via a sequence involving an intermolecular regioselective allylation of 2-azaallyl anions followed by a 2-aza-Cope rearrangement. The reaction utilizes easily available reagents and catalysts, tolerates a substantial scope of substrates, and readily leads to various enantioenriched, 1,4-disubstituted homoallylic primary amines.

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proposed reaction pathway

Key Words

homoallylic amines, Cope rearrangement

ID: J48-Y2016