S,O-Ligand Promoted meta-C–H Arylation of Anisole Derivatives via Palladium/Norbornene Catalysis

21 April 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Reversing the conventional site-selectivity of C−H activation processes provides new retrosynthetic disconnections to otherwise unreactive bonds. Here, we report the realization of non-conventional site-selectivity through Pd/Norbornene cooperative-catalysis. Specifically, we report a new catalytic system based on Pd/norbornene with an S,O-ligand for the meta-C−H arylation of aryl ethers. Furthermore, we demonstrate the unique ability of this system to employ alkoxyarene substrates bearing both electron donating and withdrawing substituents. Additionally, ortho-substituted aryl ethers are well tolerated, with the ortho constraint overcome through the use of a novel norbornene mediator. Remarkably, the monoarylation of alkoxyarenes is achieved efficiently enabling the subsequent introduction of a second, different aryl coupling partner to rapidly furnish unsymmetrical terphenyls.


C-H arylation
reverse site-selectivity

Supplementary materials

Supporting Information
Experimental procedures, compounds characterizations, crystallographic data and mechanistic studies. Crystallographic data for compound C3 have been deposited at the Cambridge Crystallo-graphic Data Centre (CCDC) under deposition no. CCDC 2128582. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.


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