School of Biological and Chemical Sciences, NUI Galway, University Road, Galway, H91 TK33, Ireland.
Unité de Chimie des Biomolécules, UMR 3523 CNRS, Institut Pasteur, Université de Paris, 28 rue du Dr Roux, 75015, Paris, France.
Chem Rec. 2021 Nov;21(11):2958-2979. doi: 10.1002/tcr.202100221. Epub 2021 Oct 28.
This personal account focuses on synthesis of polyhydroxylated piperidines, a subset of compounds within the iminosugar family. Cyclisations to form the piperidine ring include reductive amination, substitution via amines, iminium ions and cyclic nitrones, transamidification (N-acyl transfer), addition to alkenes, ring contraction and expansion, photoinduced electron transfer, multicomponent Ugi reaction and ring closing metathesis. Enantiomerically pure piperidines are obtained from chiral pool precursors (e. g. sugars, amino acids, Garner's aldehyde) or asymmetric reactions (e. g. epoxidation, dihydroxylation, aminohydroxylation, aldol, biotransformation). Our laboratory have contributed cascades based on reductive amination from glycosyl azide precursors as well as Huisgen azide-alkene cycloaddition. The latter's combination with allylic azide rearrangement has given substituted piperidines, including those with quaternary centres adjacent to nitrogen.
这篇个人述评聚焦于多羟基化哌啶类化合物的合成，这是氨基糖家族中的一个亚类。形成哌啶环的环化反应包括还原胺化、通过胺、亚胺离子和环状硝酮进行取代、转酰胺化（N-酰基转移）、与烯烃加成、环收缩和扩张、光诱导电子转移、多组分 Ugi 反应和闭环复分解。手性纯哌啶可以从手性源前体（例如糖、氨基酸、Garner 醛）或不对称反应（例如环氧化、二羟化、氨羟化、醛醇缩合、生物转化）获得。我们实验室贡献了基于糖基叠氮化物前体的还原胺化的级联反应，以及 Huisgen 叠氮化物-烯烃环加成反应。后者与烯丙基叠氮化物重排的结合，得到了取代的哌啶类化合物，包括那些在氮原子邻位具有季碳原子的化合物。
