Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles.

Author(s) Malapit, C.A.; Caldwell, D.R.; Luvaga, I.K.; Reeves, J.T.; Volchkov, I.; Gonnella, N.C.; Han, Z.S.; Busacca, C.A.; Howell, A.R.; Senanayake, C.H.
Journal Angew Chem Int Ed Engl
Date Published 2017 Jun 06
Abstract

β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.

DOI 10.1002/anie.201703471
ISSN 1521-3773
Citation Malapit CA, Caldwell DR, Luvaga IK, Reeves JT, Volchkov I, Gonnella NC, et al. Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles. Angew Chem Int Ed Engl. 2017;56(24):6999-7002.

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