Department of Chemistry & Pharmaceutical Sciences Amsterdam Institute for Molecular & Life Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1108, 1081 HZ, Amsterdam, The Netherlands.
Organic Synthesis Division Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B-2020, Antwerp, Belgium.
Chemistry. 2023 Feb 10;29(9):e202203074. doi: 10.1002/chem.202203074. Epub 2022 Dec 20.
An iron-catalysed carbene transfer reaction of diazo compounds to isocyanides has been developed. The resulting ketenimines are trapped in situ with various bisnucleophiles to access a range of densely functionalized heterocycles (pyrimidinones, dihydropyrazolones, 1H-tetrazoles) in a one-pot process. The electron-rich Hieber anion ([Fe(CO) NO] ) facilitates efficient catalytic carbene transfer from acceptor-type α-diazo carbonyl compounds to isocyanides, providing a cost-efficient and benign alternative to similar noble metal-catalysed processes. Based on DFT calculations a plausible reaction mechanism for activation of the α-diazo carbonyl carbene precursor and ketenimine formation is provided.
发展了一种铁催化的重氮化合物向异氰的卡宾转移反应。生成的烯基腙原位与各种双亲核试剂捕获，以一锅法的方式得到一系列稠合多功能杂环（嘧啶酮、二氢吡唑酮、1H-四唑）。富电子的 Hieber 阴离子([Fe(CO)NO])促进了有效催化的卡宾从受电子型α-重氮羰基化合物向异氰的转移，为类似的贵金属催化过程提供了一种经济且环境友好的替代方法。根据 DFT 计算，提供了一种合理的反应机理，用于激活α-重氮羰基卡宾前体和烯基腙的形成。
