N-Triflylphosphoramides: highly acidic catalysts for asymmetric transformations

N-Triflylphosphoramides (NTPA), have become increasingly popular catalysts in the development of enantioselective transformations as they are stronger Bronsted acids than the corresponding phosphoric acids (PA). Their highly acidic, asymmetric active site can activate difficult, unreactive substrates. In this review, we present an account of asymmetric transformations using this type of catalyst that have been reported in the past ten years and we classify these reactions using the enantio-determining step as the key criterion. This compendium of NTPA-catalysed reactions is organised into the following categories: (1) cycloadditions, (2) electrocyclisations, polyene and related cyclisations, (3) addition reactions to imines, (4) electrophilic aromatic substitutions, (5) addition reactions to carbocations, (6) aldol and related reactions, (7) addition reactions to double bonds, and (8) rearrangements and desymmetrisations. We highlight the use of NTPA in total synthesis and suggest mnemonics which account for their enantioselectivity.

Automated summary

N-Triflylphosphoramides (NTPA) have emerged as popular catalysts for enantioselective transformations due to their stronger Bronsted acid properties compared to phosphoric acids (PA). This review categorizes NTPA-catalyzed reactions based on the enantio-determining step and highlights their use in total synthesis.