LAUSR

Abstract Mollebenzylanol A, isolated in 2018, is a tyrosine phosphatase 1B inhibitor having a highly oxygenated structure, whereas mollebenzylanol B is its C15-epimer. Enantioselective total syntheses of mollebenzylanols A and B were accomplished in 13 steps and 11 steps, respectively, through an approach involving stereo-/regio-selective epoxidation, Claisen rearrangement and stereocontrolled dihydroxylation. Both target molecules were derived from a common allyl alcohol, which underwent Eschenmoser-Claisen rearrangement to eventually afford mollebenzylanol A, and was subjected to stereoselective Johnson-Claisen rearrangement to give a key intermediate for mollebenzylanol B.