Zachmann Raphael J, Fürstner Alois
Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
Chemistry. 2021 May 17;27(28):7663-7666. doi: 10.1002/chem.202101176. Epub 2021 May 1.
The newly discovered light-driven gem hydrogenation of alkynes opens an unconventional yet efficient entry into five-coordinate Grubbs-type ruthenium carbene complexes with cis-disposed chloride ligands. Representatives of this class featuring a chelate substructure formed by an iodo-substituted benzylidene unit react with (substituted) 2-isopropoxystyrene to give prototypical "second-generation" Grubbs-Hoveyda complexes for olefin metathesis. The new approach to this venerable catalyst family is safe and versatile as it uses a triple bond rather than phenyldiazomethane as the ultimate carbene source and does not require any sacrificial phosphines.
新发现的炔烃光驱动宝石氢化反应为合成具有顺式氯配体的五配位格拉布型钌卡宾配合物开辟了一条非常规但高效的途径。这类具有由碘代亚苄基单元形成的螯合亚结构的代表物与（取代的）2-异丙氧基苯乙烯反应，生成用于烯烃复分解反应的典型“第二代”格拉布-霍维达配合物。这种制备这一经典催化剂家族的新方法安全且通用，因为它使用三键而非苯基重氮甲烷作为最终的卡宾源，并且不需要任何牺牲性膦。
