Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK.
Org Biomol Chem. 2021 Nov 18;19(44):9565-9618. doi: 10.1039/d1ob01708j.
-Triflylphosphoramides (NTPA), have become increasingly popular catalysts in the development of enantioselective transformations as they are stronger Brønsted 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.
三芳基膦酰胺（NTPA）作为比相应的磷酸（PA）更强的布朗斯台德酸，已成为发展对映选择性转化的越来越受欢迎的催化剂。它们的高度酸性、不对称活性位点可以激活困难的、无反应性的底物。在这篇综述中，我们介绍了过去十年中使用这种类型的催化剂报道的不对称转化，并根据决定对映体的步骤将这些反应分类为关键标准。NTPA 催化的反应综述分为以下几类：（1）环加成反应，（2）电环化反应、多烯和相关的环化反应，（3）亚胺加成反应，（4）亲电芳香取代反应，（5）碳正离子加成反应，（6）醛醇和相关反应，（7）双键加成反应，（8）重排和去对称化反应。我们强调了 NTPA 在全合成中的应用，并提出了用于解释其对映选择性的助记符。
