title: Highly active and efficient catalysts for alkoxycarbonylation of alkenes.
abstract: Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h-1for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Kaiwu
authors.identifier: 0000-0001-6250-2629
authors.initials: K
authors.lastname: Dong
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Xianjie
authors.initials: X
authors.lastname: Fang
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Samet
authors.initials: S
authors.lastname: Gülak
authors.affiliation: Evonik Performance Materials GmbH, Paul-Baumann-Straße 1, Marl 45772, Germany.|Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Bochum 44780, Germany.
authors.forename: Robert
authors.initials: R
authors.lastname: Franke
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Anke
authors.initials: A
authors.lastname: Spannenberg
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Helfried
authors.initials: H
authors.lastname: Neumann
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Ralf
authors.initials: R
authors.lastname: Jackstell
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Beller