Metalated Nitriles:  Organolithium, -magnesium, and -copper Exchange of α-Halonitriles

Fraser F. Fleming,*† Zhiyu Zhang,† Wang Liu,† and Paul Knochel*‡
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, and Department Chemie, Ludwig-Maximilians-Universitt, Butenandtstrasse 5-13, 81377, Mnchen, Germany
J. Org. Chem., 2005, 70 (6), pp 2200–2205
DOI: 10.1021/jo047877r
Publication Date (Web): February 22, 2005
Copyright © 2005 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

,
†

 Duquesne University.

,
‡

 Ludwig-Maximilians-Universität.

, flemingf@duq.edu

Abstract

Abstract Image

α-Halonitriles react with alkyllithium, organomagnesium, and lithium dimethylcuprate reagents generating reactive, metalated nitriles. The rapid halogen−metal exchange with alkyllithium and Grignard reagents allows selective exchange in the presence of reactive carbonyl electrophiles, including aldehydes, providing a high-yielding alkylation protocol. Lithiated and magnesiated nitriles react with propargyl bromide by SN2 displacement whereas organocopper nitriles react by SN2‘ displacement, correlating with the formation of a C-metalated nitrile.

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History

  • Published In Issue March 18, 2005
  • Received November 30, 2004

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