1. Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles.
- Author
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Malapit, Christian A., Caldwell, Donald R., Luvaga, Irungu K., Reeves, Jonathan T., Volchkov, Ivan, Gonnella, Nina C., Han, Zhengxu S., Busacca, Carl A., Howell, Amy R., and Senanayake, Chris H.
- Subjects
RHODIUM catalysts ,BORONIC acids ,AROMATIC compounds ,MALONONITRILE ,INTERMEDIATES (Chemistry) ,SUBSTITUENTS (Chemistry) - 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. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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