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Omega-halonitriles: domino cyclizations to oxa- and carbocyclic nitriles
Fraser F Fleming1, Venugopal Gudipati, Omar W Steward
1Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. flemingf@duq.edu
Abstract:
t-BuOK-induced deprotonation of omega-haloalkylnitriles generates remarkably stable potassiated nitriles. In situ deprotonation and alkylation of omega-chloroalkylnitriles with aldehyde electrophiles trigger sequential nucleophilic-electrophilic alkylations generating substituted tetrahydrofuranyl and tetrahydropyranyl nitriles. Redirecting the cyclization manifold with 5-iodopentanenitrile and a ketone causes a complementary electrophilic-nucleophilic cyclization to the corresponding carbonitrile. Collectively these cyclizations provide rapid assembly of five- and six-membered oxa- and carbocyclic nitriles demonstrating the utility of omega-halonitriles in domino alkylations.