Mechanisms for Manganese(III) Oxidations with Alkenes
作者:William E. Fristad、John R. Peterson、Andreas B. Ernst、Gordon B. Urbi
DOI:10.1016/s0040-4020(01)87310-5
日期:1986.1
metal complexed organic radicals, and the importance of an oxo-centered manganese(III) triangle are discussed as they relate to the lactone annulation reaction. Single electron transfer oxidation of alkenes is described as a route toward 1,2-diacetates of alkenes within the 8.1-7.5 eV I.P. range. Three less common modes of Mn(III) reaction are discussed and compared with the two primary processes of
在乙酸锰(III)与羧酸和烯烃的反应中,已经鉴定出三个不同的过程,它们涉及烯烃和两个独立于烯烃的过程。通过产品研究,重排,稀释实验和文献动力学数据的组合,可以提出一个统一的机制图来描述这些过程。具体地,讨论了羧酸组分的α-H酸的作用,缺电子的自由基加成,金属络合的有机自由基以及以氧代为中心的锰(III)三角形的重要性,因为它们与内酯环化反应有关。烯烃的单电子转移氧化被描述为通往8.1-7.5 eV IP范围内的烯烃1,2-二乙酸酯的途径。
Metal‐Free Electrocatalytic Diacetoxylation of Alkenes
作者:Jef R. Vanhoof、Pieter J. De Smedt、Jan Derhaeg、Rob Ameloot、Dirk E. De Vos
DOI:10.1002/anie.202311539
日期:2023.12.4
A highly efficient electrocatalytic 1,2-dioxygenation of alkenes utilizing readily available materials in ambient conditions is developed. The protocol is widely applicable to aliphatic and aromatic alkenes with excellent faradaic efficiencies and yields of up to 96 %. The versatility of the method is expanded with alkenoic acids towards lactone derivatives and with other carboxylic acids like HCOOH