Remarkable stereoelectronic control in the Lewis base assisted [2,3]-rearrangement of cyclopropenylmethyl phosphinites.
A novel 2,3-rearrangement of cyclopropenylmethyl phosphinites to methylenecyclopropylphosphine oxides was demonstrated. It was found that, in striking contrast to the analogous rearrangement known for nonstrained allylic systems, this reaction does not proceed at all upon thermal activation; however, it can be efficiently mediated by Lewis bases. Unique stereoelectronic effects control the diastereoselectivity of this transformation, leading to predominant formation of the more sterically hindered products.
Rubina
Marina
M
Department of Chemistry, University of Kansas and Center for Environmentally Beneficial Catalysis, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045-7582, USA.
Woodward
Eric W
EW
Rubin
Michael
M