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Updated: Feb 25, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Catalytic Functionalization of Styrenyl Epoxides via 2-Nickela(II)oxetanes
Addison N Desnoyer1, Jialing Geng1, Marcus W Drover1
1Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada.
Abstract:
Low-valent nickel is shown to preferentially isomerize mono- or disubstituted epoxides into their corresponding aldehydes. Experiments with tetrasubstituted epoxides demonstrate that these reactions proceed via reactive 2-nickelaoxetane intermediates, and that the oxidative addition step likely occurs with retention of configuration. The monosubstituted aldehyde isomerization products were found to rapidly react with HBpin to form boronate esters. These hydroboration reactions could be performed catalytically.
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