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

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 alpha-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 alpha-allylated isocyanoacetate with a chiral quaternary carbon in a high yield.

Automated summary

Here, a mild and transition-metal-free SN2' reaction of Morita-Baylis-Hillman adducts with isocyanoacetates is reported. This reaction proceeds in a stereo- and regiospecific manner, tolerating various functionalities and providing transformable alpha-allylated isocyanoacetates with high efficiency. Preliminary studies on the asymmetric version of this reaction demonstrate ZnEt2/chiral amino alcohol combinations as an effective asymmetric catalytic system, yielding enantioenriched alpha-allylated isocyanoacetate with a chiral quaternary carbon in high yield.