@article{c26fc4ba8ed34d5a88d79e07b5ff7fcd,
title = "Catalytic Carbochlorocarbonylation of Unsaturated Hydrocarbons via C−COCl Bond Cleavage**",
abstract = "Here we report a palladium-catalysed difunctionalisation of unsaturated C−C bonds with acid chlorides. Formally, the C−COCl bond of an acid chloride is cleaved and added, with complete atom economy, across either strained alkenes or a tethered alkyne to generate new acid chlorides. The transformation does not require exogenous carbon monoxide, operates under mild conditions, shows a good functional group tolerance, and gives the isolated products with excellent stereoselectivity. The intermolecular reaction tolerates both aryl- and alkenyl-substituted acid chlorides and is successful when carboxylic acids are transformed to the acid chloride in situ. The reaction also shows an example of temperature-dependent stereodivergence which, together with plausible mechanistic pathways, is investigated by DFT calculations. Moreover, we show that benzofurans can be formed in an intramolecular variant of the reaction. Finally, derivatisation of the products from the intermolecular reaction provides a highly stereoselective approach for the synthesis of tetrasubstituted cyclopentanes.",
keywords = "Acid chlorides, CO-free, Carbonylation, Difunctionalisation, Palladium",
author = "Denton, {Elliott H.} and Lee, {Yong Ho} and Sven Roediger and Philip Boehm and Maximilian Fellert and Bill Morandi",
note = "Funding Information: The financial support by the European Research Council under the European Union's Horizon 2020 research and innovation program (Shuttle Cat, Project ID: 757608), the ETH Z{\"u}rich, the Max‐Planck‐Society, the MPI f{\"u}r Kohlenforschung, LG Chem (fellowship to Y.H.L.), the FCI (scholarships to P.B. and S.R.) and both the Cusanuswerk and Swiss–European Mobility Programme (scholarships to M.F.) are gratefully acknowledged. We thank the NMR, MS (MoBiAS), and X‐ray (SMoCC) service departments at ETH Z{\"u}rich for technical assistance. We acknowledge Laura G{\"u}rtler for reproducing results. We are also grateful to our group for critical proofreading of the manuscript. Funding Information: The financial support by the European Research Council under the European Union's Horizon 2020 research and innovation program (Shuttle Cat, Project ID: 757608), the ETH Z?rich, the Max-Planck-Society, the MPI f?r Kohlenforschung, LG Chem (fellowship to Y.H.L.), the FCI (scholarships to P.B. and S.R.) and both the Cusanuswerk and Swiss?European Mobility Programme (scholarships to M.F.) are gratefully acknowledged. We thank the NMR, MS (MoBiAS), and X-ray (SMoCC) service departments at ETH Z?rich for technical assistance. We acknowledge Laura G?rtler for reproducing results. We are also grateful to our group for critical proofreading of the manuscript. Open access funding provided by Eidgenossische Technische Hochschule Zurich. Publisher Copyright: {\textcopyright} 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",
year = "2021",
month = oct,
day = "18",
doi = "10.1002/anie.202108818",
language = "English",
volume = "60",
pages = "23435--23443",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "43",
}