Gregori Bernhard J, Schwarzhuber Felix, Pöllath Simon, Zweck Josef, Fritsch Lorena, Schoch Roland, Bauer Matthias, Jacobi von Wangelin Axel
Dept. of Chemistry, University of Hamburg, Martin Luther King Pl 6, 20146, Hamburg, Germany.
Dept. of Physics, University of Regensburg, Universitätsstraße 31, 93053, Regensburg, Germany.
ChemSusChem. 2019 Aug 22;12(16):3864-3870. doi: 10.1002/cssc.201900926. Epub 2019 Jul 25.
The stereoselective hydrogenation of alkynes constitutes one of the key approaches for the construction of stereodefined alkenes. The majority of conventional methods utilize noble and toxic metal catalysts. This study concerns a simple catalyst comprised of the commercial chemicals iron(II) acetylacetonate and diisobutylaluminum hydride, which enables the Z-selective semihydrogenation of alkynes under near ambient conditions (1-3 bar H , 30 °C, 5 mol % [Fe]). Neither an elaborate catalyst preparation nor addition of ligands is required. Mechanistic studies (kinetic poisoning, X-ray absorption spectroscopy, TEM) strongly indicate the operation of small iron clusters and particle catalysts.
炔烃的立体选择性氢化是构建立体定向烯烃的关键方法之一。大多数传统方法使用贵金属和有毒金属催化剂。本研究涉及一种由市售化学品乙酰丙酮铁（II）和氢化二异丁基铝组成的简单催化剂，该催化剂能够在接近环境条件下（1-3巴氢气，30℃，5摩尔%[铁]）实现炔烃的Z-选择性半氢化。既不需要精细的催化剂制备，也不需要添加配体。机理研究（动力学中毒、X射线吸收光谱、透射电子显微镜）有力地表明了小铁簇和颗粒催化剂的作用。
