title: 1,4-Dicarbofunctionalization of 4-Fluoroaryl Grignard and Lithium Reagents with Disubstituted Malononitriles.
abstract: An efficient one-pot 1,4-dicarbofunctionalization of 4-fluoroaryl Grignard or lithium reagents with 2,2-disubstituted malononitriles is described. The reaction proceeds by sequential transnitrilation and SNAr reactions. Commercial Grignard solutions, Grignard reagents prepared in situ by halogen/magnesium exchange with i-PrMgCl, or aryllithium reagents prepared in situ by bromine/lithium exchange with n-BuLi are compatible with the reaction conditions. Moreover, 2,2-disubstituted malononitriles of diverse structures are accommodated. The reaction provides a unique approach to 1,4-dicarbofunctionalization of activated arenes in a tandem, one-pot transformation.
authors.affiliation: Chemical Development, Boehringer Ingelheim PharmaceuticalsInc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Christian A
authors.initials: CA
authors.lastname: Malapit
authors.affiliation: Chemical Development, Boehringer Ingelheim PharmaceuticalsInc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Irungu K
authors.initials: IK
authors.lastname: Luvaga
authors.affiliation: Chemical Development, Boehringer Ingelheim PharmaceuticalsInc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Jonathan T
authors.identifier: 0000-0002-3051-3304
authors.initials: JT
authors.lastname: Reeves
authors.affiliation: Chemical Development, Boehringer Ingelheim PharmaceuticalsInc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Ivan
authors.initials: I
authors.lastname: Volchkov
authors.affiliation: Chemical Development, Boehringer Ingelheim PharmaceuticalsInc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Carl A
authors.initials: CA
authors.lastname: Busacca
authors.affiliation: Chemical Development, Boehringer Ingelheim PharmaceuticalsInc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Amy R
authors.identifier: 0000-0003-1958-6411
authors.initials: AR
authors.lastname: Howell
authors.affiliation: Chemical Development, Boehringer Ingelheim PharmaceuticalsInc. , 900 Ridgebury Road, P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
authors.forename: Chris H
authors.initials: CH
authors.lastname: Senanayake