An Air-Stable “Masked” Bis(imino)carbene: A Carbon-Based Dual Ambiphile
An Air-Stable “Masked” Bis(imino)carbene: A Carbon-Based Dual Ambiphile
复制标题
空气稳定的“掩蔽”双（亚氨基）卡宾：碳基双亲两性化合物
DOI：
10.1021/jacs.2c12847
复制
发表时间：
2023
影响因子：
15
通讯作者：
Bertrand, Guy
中科院分区：
文献类型：
--
作者：
Loh, Ying Kai;Melaimi, Mohand;Munz, Dominik;Bertrand, Guy
卡宾，曾经被认为是实验室的好奇心，现在是化学和材料科学的有力工具。到目前为止，所有稳定的单重态卡宾都是单位两亲分子。本文描述了一种碳基双亲分子（单中心和双中心）卡宾的合成。关键是采用衍生自环状（烷基）（氨基）卡宾（CAAC）的亚氨基取代基，其赋予卡宾1，3-偶极特性。它的双重双亲性与以1，1-和1，3-方式激活简单有机分子的能力一致。此外，它的1，3-双亲性促进了与近端芳烃取代基的前所未有的可逆的分子内脱芳[3 + 2]环加成，使卡宾能够“掩盖”自身作为空气稳定的环加成物。我们认为dualambiphilicity的概念为未来的卡宾化学开辟了一个新的维度，扩展了经典单位点两亲卡宾的应用范围。
Carbenes, once considered laboratory curiosities, now serve as powerful tools in the chemical and material sciences. To date, all stable singlet carbenes are single-site ambiphiles. Here we describe the synthesis of a carbene which is a carbon-baseddualambiphile (both single-siteanddual-site). The key is to employ imino substituents derived from a cyclic (alkyl)(amino)carbene (CAAC), which imparts a 1,3-dipolar character to the carbene. Itsdualambiphilic nature is consistent with the ability to activate simple organic molecules in both 1,1- and 1,3-fashion. Furthermore, its 1,3-ambiphilicity facilitates an unprecedented reversible intramolecular dearomative [3 + 2] cycloaddition with a proximal arene substituent, giving the carbene the ability to “mask” itself as an air-stable cycloadduct. We perceive that the concept ofdualambiphilicity opens a new dimension for future carbene chemistry, expanding the repertoire of applications beyond that known for classical single-site ambiphilic carbenes.