title: The scope and mechanism of palladium-catalysed Markovnikov alkoxycarbonylation of alkenes.
abstract: Hydroesterification reactions represent a fundamental type of carbonylation reaction and constitute one of the most important industrial applications of homogeneous catalysis. Over the past 70 years, numerous catalyst systems have been developed that allow for highly linear-selective (anti-Markovnikov) reactions and are used in industry to produce linear carboxylates starting from olefins. In contrast, a general catalyst system for Markovnikov-selective alkoxycarbonylation of aliphatic olefins remains unknown. In this paper, we show that a specific palladium catalyst system consisting of PdX2/N-phenylpyrrole phosphine (X, halide) catalyses the alkoxycarbonylation of various alkenes to give the branched esters in high selectivity (branched selectivity up to 91%). The observed (and unexpected) selectivity has been rationalized by density functional theory computation that includes a dispersion correction.
authors.affiliation: Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein Straße 29a, Rostock 18059, Germany.
authors.forename: Haoquan
authors.initials: H
authors.lastname: Li
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: Haijun
authors.initials: H
authors.lastname: Jiao
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