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Enantioselective Olefin Hydrocyanation Without Cyanide

preprint
submitted on 18.10.2019 and posted on 23.10.2019 by Alexander Schuppe, Gustavo M. Borrajo-Calleja, Stephen L. Buchwald
The enantioselective hydrocyanation of olefins represents a conceptually straightforward approach to prepare enantiomerically enriched nitriles. These, in turn, comprise or are intermediates in the synthesis of many pharmaceuticals and their synthetic derivatives. Herein, we report a cyanide-free dual Pd/CuH-catalyzed protocol for the asymmetric Markovnikov hydrocyanation of vinyl arenes and the anti-Markovnikov hydrocyanation of terminal olefins in which oxazoles function as nitrile equivalents. After an initial hydroarylation process, the oxazole substructure was deconstructed using a [4+2]/retro-[4+2] sequence to afford the enantioenriched nitrile product under mild reaction conditions.

History

Email Address of Submitting Author

aschuppe@mit.edu

Institution

Massachusetts Institute of Technology

Country

United States

ORCID For Submitting Author

0000-0001-6002-9110

Declaration of Conflict of Interest

MIT has obtained patents for some of the ligands that are described in this Communication from which S.L.B. and former/current co-workers receive royalty payments.

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in Journal of the American Chemical Society

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