WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
Angew Chem Int Ed Engl. 2017 Jun 1;56(23):6632-6635. doi: 10.1002/anie.201702246. Epub 2017 May 10.
Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me C H )CH } ]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH SiMe ) and Al(TMP)iBu ), key intermediates in this process have been isolated and structurally defined.
结合碱金属介导的金属化（AMMM）和 N-杂环卡宾（NHC）化学，本文描述了一种新型的 C-N 键活化和开环反应，用于这些日益重要的 NHC 分子，这些分子通常被认为是坚固的辅助配体。在这里，对饱和 NHC SIMes（SIMes=[:C{N(2,4,6-MeC H )CH } ]）与第 1 族烷基碱反应的机理研究表明，这个破坏性过程是由卡宾的侧向金属化引发的。利用与低极性有机金属试剂（Mg(CHSiMe )和 Al(TMP)iBu）的共络合和反金属捕获策略，该过程中的关键中间体已被分离并进行了结构定义。
