Latent Pronucleophiles in Lewis Base Catalysis: Enantioselective Allylation of Silylated Stabilized Carbon Nucleophiles with Allylic Fluorides

Abstract

Lewis base catalyzed allylations of C-centered nucleophiles have been largely limited to the niche substrates with acidic C-H substituted with C-F bonds at the stabilized carbanionic carbon. Here we report that the concept of latent pronucleophiles serves to overcome these limitations and allow for a variety of common silylated stabilized C-nucleophiles to undergo enantioselective allylations using allylic fluorides. The reactions of silyl enol ethers afford the allylation products in good yields and with high degree of regio / stereoselectivity as well as diastereoselectivity when cyclic silyl enol ethers are used. Further examples of silylated stabilized carbon nucleophiles that undergo efficient allylation speak in favor of the broad applicability of this concept in the arena of C-centered nucleophiles.