Nickel-Catalyzed Inter- and Intramolecular Aryl Thioether Metathesis by Reversible Arylation.

Angew Chem Int Ed Engl

Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093, Zürich, Switzerland.

Published: January 2020

A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni /Ni pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7004142PMC
http://dx.doi.org/10.1002/anie.201910436DOI Listing

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