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Updated: Aug 18, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Reaction of metalated nitriles with enones
Hans J Reich1, Margaret M Biddle, Robert J Edmonston
1Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA. reich@chem.wisc.edu
Abstract:
[reaction: see text] There have been a number of reports of the kinetic conjugate (1,4) addition of metalated arylacetonitriles to enones. Several proposals have been made to explain this behavior based on nucleophile structure or aggregation state or on the HSAB properties of the reactants. A reexamination of these studies showed that in each case the 1,4 adducts resulted from equilibration of the kinetically formed 1,2 adducts to the more stable 1,4 adducts. Thus, no conclusions about the origins of 1,4 selectivity can be drawn from these experiments. The 1,2 addition, retro-1,2 addition, 1,4 addition, and retro-1,4 addition of lithiophenylacetonitrile to benzylideneacetone were examined, and a free energy level diagram was constructed for the reaction.
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