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[gamma]- and [d]-Hydroxynitriles: diastereoselective electrophile-dependent alkylations
Journal article   Peer reviewed

[gamma]- and [d]-Hydroxynitriles: diastereoselective electrophile-dependent alkylations

Robert Mycka, William Eckenhoff, Omar Steward, Nathan Barefoot and Fraser Fleming
Tetrahedron, v 69(1), pp 366-376
07 Jan 2013

Abstract

Alkylation Asymmetry Chelating Nitriles Tetrahedrons
Deprotonating [gamma]- and [d]-hydroxynitriles with i-PrMgCl allows highly diastereoselective alkylations controlled by the asymmetry of the remote carbinol stereocenter. Mechanistic experiments are consistent with [gamma]-hydroxynitriles alkylating via a chelated magnesiated nitrile whereas [d]-hydroxynitriles favor alkylation from acyclic magnesiated nitriles. Collectively these alkylations; are the first electrophile-dependent alkylations of acyclic nitriles, exhibit a unique influence on the nature of the Grignard used for the deprotonation, and address the challenge of installing quaternary centers in conformationally mobile, acyclic nitriles.

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Web of Science research areas
Chemistry, Organic
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