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钯催化烯烃与绿色氧化剂的氧化反应

Palladium-Catalyzed Oxidation Reactions of Alkenes with Green Oxidants.

作者信息

Hu Miao, Wu Wanqing, Jiang Huanfeng

机构信息

Key Laboratory of Functional Molecular Engineering of, Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Guangzhou, 510640, PR China.

出版信息

ChemSusChem. 2019 Jul 5;12(13):2911-2935. doi: 10.1002/cssc.201900397. Epub 2019 Jun 24.

Abstract

Transition-metal-catalyzed oxidative functionalization of alkenes has emerged as a powerful and valuable tool in modern organic synthesis. Recently, many methods have been established for the assembly of C-C and C-heteroatom bonds, which provides tremendous possibility for application in biology, medicine, and materials science. However, the use of stoichiometric amounts of strong oxidants leads to poor selectivity, low atom economy, and a series of undesired waste products. By contrast, green oxidants, such as O , H O , or tert-butyl hydroperoxide (TBHP), have bright prospects due to their attributes of mild, low cost, and great sustainability in transition-metal-catalyzed oxidation reactions. Based on the great and unique potential for the development of aerobic reactions, this review mainly highlights homogenous palladium-catalyzed green oxidations of alkenes that have been reported in recent years. These methods provide new strategies for the transformation and functionalization of alkenes; some of them have also been successfully applied to the synthesis of the core structures of drugs and natural products. Additionally, through in-depth studies of the reaction mechanisms in this field, it is believed that palladium-catalyzed green oxidation reactions of alkenes with O , H O , or TBHP will create added value for organic synthetic chemistry.

摘要

过渡金属催化的烯烃氧化官能团化反应已成为现代有机合成中一种强大且有价值的工具。最近,已建立了许多用于构建碳 - 碳键和碳 - 杂原子键的方法,这为其在生物学、医学和材料科学中的应用提供了巨大的可能性。然而,使用化学计量的强氧化剂会导致选择性差、原子经济性低以及产生一系列不需要的废弃物。相比之下,绿色氧化剂,如氧气、过氧化氢或叔丁基过氧化氢(TBHP),由于其在过渡金属催化氧化反应中具有温和、低成本和高可持续性的特点,具有广阔的前景。基于有氧反应发展的巨大且独特的潜力,本综述主要重点介绍近年来报道的均相钯催化的烯烃绿色氧化反应。这些方法为烯烃的转化和官能团化提供了新策略;其中一些方法还已成功应用于药物和天然产物核心结构的合成。此外,通过对该领域反应机理的深入研究,人们认为钯催化的烯烃与氧气、过氧化氢或叔丁基过氧化氢的绿色氧化反应将为有机合成化学创造附加值。

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