The exceptional chelating ability of dimethylaluminum chloride and methylaluminum dichloride. The merged stereochemical impact of alpha- and beta-stereocenters in chelate-controlled carbonyl addition reactions with enolsilane and hydride nucleophiles

A systematic investigation of the stereoselectivity in Lewis acid-promoted (Mukaiyama) aldol reactions of achiral unsubstituted enolsilanes and chiral beta -hydroxy aldehydes proceeding under conditions favoring chelation con trol is presented. Good stereocontrol can be realized for enolsilane aldol reactions of beta -alkoxy and beta -silyloxy aldehydes bearing only an alph a- or a beta -stereogenic center. Examination of the chelated intermediates for alpha,beta -disubstituted aldehydes concludes that the syn aldehyde di astereomer possesses the arrangement of stereocenters wherein the alpha- an d beta -substituents impart a reinforcing facial bias upon the aldehyde car bonyl. Aldol reactions of syn aldehydes were thus observed to proceed with uniformly excellent diastereofacial selectivity. Aldol reactions of the cor responding anti aldehydes containing opposing stereocontrol elements at the alpha- and beta -positions exhibit variable and unpredictable selectivity.