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一氧化二氮催化合成苯酚
作者:小柯机器人 发布时间:2022/4/30 23:08:06

德国马克斯·普朗克煤炭研究所Cornella, Josep团队报道了一氧化二氮催化合成苯酚。相关研究成果于2022年4月27日发表于国际顶尖学术期刊《自然》。

一氧化二氮(N2O)再价化催化化学过程的开发,是缓解其排放造成环境威胁的一个有吸引力的策略。传统上,N2O被认为是一种惰性分子,作为氧化剂或O-原子转移试剂,有机化学家难以处理,因为其活化所需的苛刻条件(>150°C,50200bar)。

该文中,研究人员报告了在温和的条件下(室温,1.5–2bar N2O),N2O插入到NiC键中,从而提供有价值的酚并释放出良性的N2。这种完全不同的有机金属共键形成步骤不同于当前基于还原消除的策略,并为芳基卤化物转化为苯酚提供了一种替代催化方法。该过程通过镍中心的联吡啶配体进行催化。该方法具有鲁棒性、温和性和高度选择性,能够适应碱敏感功能,并能够从高度功能化的芳基卤化物合成苯酚。尽管本策略并未提供缓解N2O排放的解决方案,但它代表了丰富的N2O作为一种O源进行温和再加热的反应性蓝图。

附:英文原文

Title: Catalytic synthesis of phenols with nitrous oxide

Author: Le Vaillant, Franck, Mateos Calbet, Ana, Gonzlez-Pelayo, Silvia, Reijerse, Edward J., Ni, Shengyang, Busch, Julia, Cornella, Josep

Issue&Volume: 2022-04-27

Abstract: The development of catalytic chemical processes that enable the revalorization of nitrous oxide (N2O) is an attractive strategy to alleviate the environmental threat posed by its emissions1,2,3,4,5,6. Traditionally, N2O has been considered an inert molecule, intractable for organic chemists as an oxidant or O-atom transfer reagent, owing to the harsh conditions required for its activation (>150°C, 50200bar)7,8,9,10,11. Here we report an insertion of N2O into a NiC bond under mild conditions (room temperature, 1.5–2bar N2O), thus delivering valuable phenols and releasing benign N2. This fundamentally distinct organometallic CO bond-forming step differs from the current strategies based on reductive elimination and enables an alternative catalytic approach for the conversion of aryl halides to phenols. The process was rendered catalytic by means of a bipyridine-based ligands for the Ni centre. The method is robust, mild and highly selective, able to accommodate base-sensitive functionalities as well as permitting phenol synthesis from densely functionalized aryl halides. Although this protocol does not provide a solution to the mitigation of N2O emissions, it represents a reactivity blueprint for the mild revalorization of abundant N2O as an O source.

DOI: 10.1038/s41586-022-04516-4

Source: https://www.nature.com/articles/s41586-022-04516-4

期刊信息

Nature:《自然》,创刊于1869年。隶属于施普林格·自然出版集团,最新IF:42.778
官方网址:http://www.nature.com/