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

Abstract

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 regio­selectivity 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

Key words

Lewis base catalysis - enantioselective catalysis - organocatalysis, latent nucleophiles - latent pronucleophiles - allylic substitutions

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