Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Strasse 29a, 18059, Rostock, Germany.
Evonik Performance Materials GmbH, Paul-Baumann-Strasse 1, 45772, Marl, Germany.
Angew Chem Int Ed Engl. 2017 May 2;56(19):5267-5271. doi: 10.1002/anie.201700317. Epub 2017 Mar 30.
The development of ligands plays a key role and provides important innovations in homogeneous catalysis. In this context, we report a novel class of ferrocenyl phosphines for the alkoxycarbonylation of industrially important alkenes. A basic feature of our ligands is the combination of sterically hindered and amphoteric moieties on the P atoms, which leads to improved activity and productivity for alkoxycarbonylation reactions compared to the current industrial state-of-the-art ligand 1,2-bis((di-tert-butylphosphino)methyl)benzene). Advantageously, palladium catalysts with these novel ligands also enable such transformations without additional acid under milder reaction conditions. The practicability of the optimized ligand was demonstrated by preparation on >10 g scale and its use in palladium-catalyzed carbonylations on kilogram scale.
配体的发展起着关键作用，并为均相催化提供了重要的创新。在这方面，我们报告了一类新型的二茂铁基膦配体，用于工业上重要的烯烃的烷氧基羰基化反应。我们配体的一个基本特点是在磷原子上结合了空间位阻和亲核性部分，这导致与当前工业最先进的配体 1,2-双((二-叔丁基膦基)甲基)苯相比，烷氧基羰基化反应的活性和产率得到了提高。有利的是，带有这些新型配体的钯催化剂也能够在更温和的反应条件下，在没有额外酸的情况下进行这些转化。通过在 >10 g 规模上的制备和在公斤规模上的钯催化羰基化反应中的应用，优化配体的实用性得到了证明。
