Stereo- and Regiospecific SN2' Reaction of MBH Adducts with Isocyanoacetates: en Route to Transition-Metal-Free α-Allylation of Isocyanoacetates.

ABSTRACT

Herein, we report that under mild and transition-metal-free conditions an unprecedented and practical SN2' reaction of Morita-Baylis-Hillman adducts with isocyanoacetates takes place in a stereo- and regiospecific manner. This reaction which tolerates a wide variety of functionalities delivers transformable α-allylated isocyanoacetates in high efficiencies. Preliminary studies on the asymmetric version of this reaction indicate that ZnEt2/chiral amino alcohol combinations are an asymmetric catalytic system for this transformation, giving an enantioenriched α-allylated isocyanoacetate with a chiral quaternary carbon in a high yield.