Financial support from Carl-Zeiss Foundation (Carl-Zeiss-Stiftung endowed professorship to I.V.), Friedrich Schiller University Jena and State of Thuringia (fellowship to M.L.) is gratefully acknowledged.
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
20 There will be examples where latency related to the presence of the silyl group is relevant in reaction development, which is why term ‘latent pronucleophile’ is more accurate than the simple term ‘pronucleophile’. These examples are not described here and go beyond the scope of the current discussion.
21
Purser S,
Moore PR,
Swallow S,
Gouverneur V.
Chem. Soc. Rev. 2008; 37: 320
