Fluoride-catalyzed aldol reaction of ethyl trimethylsilyldiazoacetate with aldehydes leading to ethyl α-diazo-β-hydroxy esters and rhodium catalyzed decarboxylative rearrangement of diazo urethanes leading to β- amino acrylates

Article abstract of DOI:10.1016/S0040-4039(99)00933-8

Ethyl trimethylsilyldiazoacetate reacts smoothly with a variety of aldehydes at 0 °C in the presence of a catalytic amount of tetrabutylammonium fluoride to produce α-diazo-β-hydroxy esters in good to excellent yields. The resulting α-diazo-β-hydroxy esters can be stereoselectively transformed, by a sequence of carbamation with p- toluenesulfonyl isocyanate and rhodium(II)-induced decarboxylative rearrangement, to α- or β-substituted β-(p-toluenesulfonylamino)acrylates depending upon migration aptitude of the substituents derived from the aldehydes.