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羰基化合物的电化学脱饱和
作者:小柯机器人 发布时间:2021/3/28 15:29:01

美国斯克里普斯研究所Phil S. Baran团队揭示了一种羰基化合物的电化学脱饱和反应。 相关研究成果于2021年3月23日发表于国际一流学术期刊《自然-化学》。

电化学技术长期以来一直被认为是实现氧化还原反应的有效方法。羰基去饱和作为一种基本的有机氧化反应,是一种常用的通过去除两个氢原子来释放相邻反应性的转化反应。迄今为止,实现这一看似微不足道的反应的最可靠方法依赖于过渡金属(Pd或Cu)或基于I、Br、Se或S的化学计量试剂。

该文中,研究人员报告了一种操作简单的途径,使用电子作为主要试剂从烯醇硅烷和磷酸盐中获得此类结构。这种电化学驱动的去饱和反应在一系列羰基衍生物中表现出广泛的范围,易于扩展(1–100g),并且可以通过实验或计算得出的核磁共振位移预测地实现到合成途径中。与最新技术的系统比较表明,这种方法是唯一地可以使大量羰基脱饱和的方法。机械的询问表明了一种基于自由基的反应途径。

附:英文原文

Title: Electrochemically driven desaturation of carbonyl compounds

Author: Samer Gnaim, Yusuke Takahira, Henrik R. Wilke, Zhen Yao, Jinjun Li, Dominique Delbrayelle, Pierre-Georges Echeverria, Julien C. Vantourout, Phil S. Baran

Issue&Volume: 2021-03-23

Abstract: Electrochemical techniques have long been heralded for their innate sustainability as efficient methods to achieve redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity through the formal removal of two hydrogen atoms. To date, the most reliable methods to achieve this seemingly trivial reaction rely on transition metals (Pd or Cu) or stoichiometric reagents based on I, Br, Se or S. Here we report an operationally simple pathway to access such structures from enol silanes and phosphates using electrons as the primary reagent. This electrochemically driven desaturation exhibits a broad scope across an array of carbonyl derivatives, is easily scalable (1–100g) and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Systematic comparisons to state-of-the-art techniques reveal that this method can uniquely desaturate a wide array of carbonyl groups. Mechanistic interrogation suggests a radical-based reaction pathway.

DOI: 10.1038/s41557-021-00640-2

Source: https://www.nature.com/articles/s41557-021-00640-2

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex