LAQV-REQUIMTE, University of Évora, Institute for Research and Advanced Training (IIFA), Rua Romão Ramalho, Évora, Portugal.
Department of Chemistry, School of Science and Technology, University of Évora, Évora, Portugal and Instituto Universitario de Bio-Orgánica "Antonio González" (IUBO-AG), University of la laguna, Tenerife, Spain.
Chem Commun (Camb). 2021 Mar 11;57(21):2585-2590. doi: 10.1039/d0cc07905g.
The benzilic acid rearrangement (BAR) is the oldest rearrangement on record. It is a powerful synthetic tool for accessing significant biologically active molecules. The reaction is both catalytic (generally Lewis acid) and stereoselective, recently the first catalytic asymmetric version was reported with astonshing results (ees of up to 97%) to give chiral tartronic esters. In this unique highlight, we look at the progress made over the last 10 years on the stereoseletive aspects of this synthetic transformation, showing interesting examples of this rearrangment in both acyclic and cyclic systems (like for instance its importance in the stereoselective synthesis of syn and anti-hydroxy-iso-evoninic acids, α-hydroxy-α-perfluoroalkyl esters, a selective nonsteroidal mineralocorticoid receptor antagonist, Geldanamycin type polyketides and (-)-isatisine A, etc.) and the differnces in stereoselectivity encountered which culminated recently in the conquest of the first catalytic asymmetric example on record.
苯偶姻重排（BAR）是有记录以来最古老的重排反应。它是一种强大的合成工具，可用于获取具有重要生物活性的分子。该反应具有催化（通常为路易斯酸）和立体选择性，最近首次报道了具有惊人结果（ee 值高达 97%）的催化不对称版本，可得到手性酒石酸酯。在这个独特的亮点中，我们回顾了过去 10 年在这种合成转化的立体选择性方面取得的进展，展示了在无环和环状系统中该重排的有趣实例（例如，它在手性合成 syn 和 anti-羟基异依康酸、α-羟基-α-全氟烷基酯、选择性非甾体盐皮质激素受体拮抗剂、Geldanamycin 型聚酮和（-）靛红 A 等方面的重要性）以及最近在首例催化不对称实例中遇到的立体选择性差异，最终实现了首例记录。
