Conversion of alpha-haloaldehydes into acylating agents by an internal redox reaction catalyzed by nucleophilic carbenes.
Reactivity umpolung allows us to consider nontraditional bond disconnections. We report herein that treatment of an alpha-haloaldehyde with a nucleophile in the presence of catalytic amounts of nucleophilic carbenes results in an internal redox reaction giving rise to a dehalogenated acylating agent as an intermediate by a new reaction manifold. A brief illustration of the scope of this reaction is presented along with evidence supporting the direct intervention of the carbene in the acylation step.
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
Nathan T
NT
Reynolds
Javier
J
Read de Alaniz
Tomislav
T
Rovis