Stereo- and Regiospecific S(N)2' Reaction of MBH Adducts with Isocyanoacetates: en Route to Transition-Metal-Free α-Allylation of Isocyanoacetates

MBH加合物与异氰基乙酸酯的立体选择性和区域选择性S(N)2'反应:通往异氰基乙酸酯无过渡金属α-烯丙基化之路

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Abstract

Herein, we report that under mild and transition-metal-free conditions an unprecedented and practical S(N)2' 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 ZnEt(2)/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.

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