These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
2 files

Enantioselective Olefin Hydrocyanation Without Cyanide

submitted on 18.10.2019, 15:22 and posted on 23.10.2019, 15:18 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.


Email Address of Submitting Author


Massachusetts Institute of Technology


United States

ORCID For Submitting Author


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.


Read the published paper

in Journal of the American Chemical Society

Logo branding