Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
Jonathan T. Reeves*, Christian A. Malapit, Frederic G. Buono, Kanwar P. Sidhu, Maurice A. Marsini, C. Avery Sader, Keith R. Fandrick, Carl A. Busacca and Chris H. Senanayake
*Chemical Development, Boehringer Ingelheim Pharmaceuticals,
Inc., 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368,
United States, Email: jonathan.reeves
boehringer-ingelheim.com
J. T. Reeves, C. A. Malapit, F. G. Buono, K. P. Sidhu, M. A. Marsini, C. A. Sader, K. R. Fandrick, C. A. Busacca, C. H. Senanayake, J. Am. Chem. Soc., 2015, 137, 9481-9488.
DOI: 10.1021/jacs.5b06136
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Abstract
The commercially available, bench-stable dimethylmalononitrile (DMMN) enables an electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates.
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Key Words
ID: J48-Y2015
