Catalytic Carbochlorocarbonylation of Unsaturated Hydrocarbons via C−COCl Bond Cleavage

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 transformatio...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2021-10, Vol.60 (43), p.23435-23443
Main Authors: Denton, Elliott H., Lee, Yong Ho, Roediger, Sven, Boehm, Philip, Fellert, Maximilian, Morandi, Bill
Format: Article
Language:English
Subjects:
Acid chlorides
Acids
Alkenes
Alkynes
Atom economy
Carbon monoxide
Carbonylation
Carboxylic acids
Chlorides
CO-free
Difunctionalisation
Functional groups
Palladium
Stereoselectivity
Temperature dependence
Unsaturated hydrocarbons
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Summary: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. Using a catalytic system comprised of Pd and Xantphos, acid chlorides can be added across strained alkenes or tethered alkynes to form two new C−C bonds via formal C−COCl cleavage. This reaction allows for a dicarbofunctionalisation in which an acid chloride group is retained in the product. DFT studies are used to rationalise a plausible pathway, while product derivatisation highlights the synthetic utility of the method.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202108818