Chen Yang, Zhu Shifa
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, P. R. China.
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China.
Chem Commun (Camb). 2024 Oct 3;60(80):11253-11266. doi: 10.1039/d4cc03252g.
As has been well-recognized, the semipinacol rearrangements (SPRs) function as a powerful and versatile tool for the construction of all-carbon and heteroatom-containing quaternary stereocenters, which are present in various natural products and bioactive molecules. In recent years, considerable attention has been paid to exploring the metal carbene-induced semipinacol rearrangements, providing an attractive and powerful strategy for obtaining various important carbonyl compounds. However, to date, no review has been published that summarizes the significant advances in the preparation of functionalized carbonyl compounds using these migration rearrangement reactions. In this review article, we have summarised the recent advances in the field of metal carbene-induced SPR reactions according to different metal classifications. Mechanistic insights, synthetic applications, and their limitations are discussed. The challenges and opportunities in this field are also outlined.
众所周知，半频哪醇重排反应（SPRs）是构建全碳和含杂原子季碳立体中心的一种强大且通用的工具，这些立体中心存在于各种天然产物和生物活性分子中。近年来，人们对探索金属卡宾诱导的半频哪醇重排反应给予了相当大的关注，为获得各种重要的羰基化合物提供了一种有吸引力且强大的策略。然而，迄今为止，尚未发表过综述来总结利用这些迁移重排反应制备功能化羰基化合物方面的重大进展。在这篇综述文章中，我们根据不同的金属分类总结了金属卡宾诱导的SPRs反应领域的最新进展。讨论了反应机理、合成应用及其局限性。还概述了该领域的挑战和机遇。
