Opening of Tartrate Acetals Using Dialkylboron Bromide: Evidence for Stereoselectivity Downstream from Ring Fission

Johnson-type acetals derived from dimethyl tartrate give, after opening with Me2BBr and cuprate displacement, secondary alcohols with high diastereoselectivity (>30:1). The mechanism proposed for the induction of diastereoselectivity is downstream from the ring fission. It implies a direct participation of the Lewis acid as a source of nucleophile and the stereospecific transformation of the resulting bromo acetal through an invertive and temperature-dependent process. The acetals are prepared by reaction of the desired aldehyde with dimethyl tartrate. Removal of the auxiliary is accomplished through SmI2 reduction or by an addition−elimination protocol using methoxide.