1.
Org Lett
; 22(13): 5170-5175, 2020 Jul 02.
Article
in English
| MEDLINE
| ID: mdl-32610917
ABSTRACT
A stereoselective transformation of α,ß-epoxyketones into alkenylphosphates having a hydroxymethyl group on the ß-carbon was established by utilizing the [1,2]-phospha-Brook rearrangement under Brønsted base catalysis. The reaction involves the catalytic generation of an α-oxygenated carbanion located at the α-position of an epoxide moiety through the [1,2]-phospha-Brook rearrangement and the following epoxide opening. Further transformation of the alkenylphosphates by the palladium-catalyzed cross-coupling reaction with Grignard reagents provided allylic alcohols having a stereodefined all-carbon tetrasubstituted alkene moiety.