Latent (Pro)Nucleophiles in Enantioselective Lewis Base Catalyzed Allylic Substitutions

The use of latent nucleophiles, which are molecules that are not nucleophilic but can be activated to act as a nucleophile at an opportune time during the reaction, expands the scope of Lewis base catalyzed reactions. Here, we provide an overview of the concept and show examples of applications to N- and C-centered nucleophiles in allylic substitutions. N- and C-silyl compounds are superior latent (pro)nucleophiles in Lewis base catalyzed reactions with allylic fluorides in which the formation of the strong Si-F bond serves as the driving force for the reactions. The latent (pro)nucleophiles ensure high regio-selectivity in these reactions and enable enantioselective transformations of Morita-Baylis-Hillman adducts by the use of common chiral Lewis base catalysts. 1 Introduction 2 Substitution of MBH Carbonates 3 The Concept of Latent (Pro)Nucleophiles 4 Enantioselective Allylation of N-Heterocycles 5 Enantioselective Phosphonyldifluoromethylation of Allylic Fluorides 6 Conclusion