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J Am Chem Soc. 2019 Nov 20;141(46):18475-18485. doi: 10.1021/jacs.9b07607. Epub 2019 Oct 30.

Directed Copper-Catalyzed Intermolecular Aminative Difunctionalization of Unactivated Alkenes.

Author information

1
Key Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology , Peking University Shenzhen Graduate School , Shenzhen 518055 , China.

Abstract

A diverse collection of copper-catalyzed intermolecular aminative difunctionalizations of unactivated alkenes with N-halodialkylamines as the terminal dialkylamino source is reported. A bidentate auxiliary tethered on the alkene substrates is crucial, which can promote the migratory insertion of nonactivated alkenes into the aminyl radical-metal complex and stabilize the resultant high-valent copper intermediate to allow for further transformations. By employing this strategy, the intermolecular aminohalogenation reactions and a three-component aminoazidation reaction of unactivated alkenes with dialkylamino source were successively achieved in a remarkable regio- and stereoselective manner. These reactions were performed under neutral conditions and maintained excellent functional group tolerance toward a wide range of N-halodialkylamines and unactivated alkenes. Further mechanistic studies and DFT calculations supported a concerted migratory insertion of the C-C double bond into the aminyl radical-metal complex to form a Cu(III) intermediate.

PMID:
31600069
DOI:
10.1021/jacs.9b07607

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