四川大学王天利团队报道了通过肽模拟磷盐催化的不对称好氧羟基化反应获得对映体富集的烯丙醇。相关研究成果于2024年4月29日发表于国际顶尖学术期刊《中国化学》。

从学术和工业角度来看，开发能够获得增值功能或结构的催化不对称方法，例如烯丙醇，是一个非常有趣但具有挑战性的课题。然而，在化学催化的最新进展之前，构建对映体富集的叔烯丙醇支架的方案很少。

在这种情况下，研究人员发现肽模拟鏻盐在α，β-不饱和和/或β，-不饱和化合物的催化不对称α-羟基化中高效，具有令人满意的区域和立体化学结果（高达97%的产率和95%的ee）。

该方法耐受广泛的底物，因此能够避免使用额外的还原剂和昂贵的金属催化剂，为组装对映体富集的叔烯丙醇提供了一个快速而统一的平台。此外，通过简单的条件和使用空气作为羟基官能团的来源，扩大了该方案的应用。

附：英文原文

Title: Access to Enantioenriched Allylic Alcohols via Peptide-Mimic Phosphonium Salt-Catalyzed Asymmetric Aerobic Hydroxylation

Author: Jixing Che, Siqiang Fang, Zanjiao Liu, Jiajia He, Jia-Yan Zheng, Fan Wang, Tianli Wang

Issue&Volume: 2024-04-29

Abstract: The development of catalytic asymmetric methods that enable access to value-added functionalities or structures, exemplified by allylic alcohols, is a highly interesting yet challenging topic from both academic and industrial perspectives. However, before recent advances in chemical catalysis, there were scarce protocols toward constructing enantioenriched tertiary allylic alcohol scaffolds. In this context, peptide-mimic phosphonium salts were found to be highly efficient in catalytic asymmetric α-hydroxylation of α,β-unsaturated and/or β,-unsaturated compounds with satisfactory regio- and stereochemical outcomes (up to 97% yield and 95% ee). This methodology tolerates a broad array of substrates and thus provides an expeditious and unified platform for the assembly of enantioenriched tertiary allylic alcohols by avoiding the use of additional reductants and expensive metal catalysts. Furthermore, the power of this protocol is enlarged by simple conditions and the use of air as a source of hydroxyl functionality.

DOI: 10.1002/cjoc.202400245

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202400245