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Catalytic, Enantioselective Syn-Diamination of Alkenes

preprint
submitted on 23.09.2019 and posted on 26.09.2019 by Zhonglin Tao, Brad Gilbert, Scott Denmark
The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this Article we describe the first enantioselective, syn-diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a N,N’-bistosyl urea as the bifunctional nucleophile and N-fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities selectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the syn-dichlorination reported previously. Furthermore, the syn-stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.

Funding

National Science Foundation CHE1664376

History

Email Address of Submitting Author

sdenmark@illinois.edu

Institution

University of Illinois at Urbana-Champaign

Country

USA

ORCID For Submitting Author

0000-0002-1099-9765

Declaration of Conflict of Interest

No conflict of interest

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in Journal of the American Chemical Society

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