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DOI: 10.1055/s-0037-1611482
Access to Biphenyls by Palladium-Catalyzed Oxidative Coupling of Phenyl Carbamates and Phenols
This project was supported by the Deutsche Forschungsgemeinschaft (Ba 1372-19/1) and by the Graduate School, Technische Universität München.Publikationsverlauf
Received: 14. März 2019
Accepted: 19. März 2019
Publikationsdatum:
15. April 2019 (online)

Abstract
The oxidative cross-coupling of phenols (3 equiv) to various substituted phenyl N,N-diethylcarbamates was explored with a variety of substrates. Pd(OAc)2 was employed as the catalyst (20 mol%) and K2S2O8 as the stoichiometric oxidant in trifluoroacetic acid as the solvent (50 °C, 2 h). Carbamates without or with a substituent on the phenyl ring (Me, Ph, Cl, OMe) underwent the reaction unless the phenyl substituent was too strongly electron withdrawing (CN). Cross-coupling occurred exclusively in the ortho position relative to the carbamate group. The regioselectivity at the phenol (ortho or para to hydroxy) was mainly determined by steric factors. Yields up to 60–70% were achieved for specific carbamate/phenol combinations.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611482.
- Supporting Information
Primary Data
- Primary Data
Primary data for this article are available online at https://zenodo.org/record/4637081 and can be cited using the following DOI: 10.5281/zenodo.4610538. Please note that the DOI for the Primary Data associated with this article was updated on April 19, 2021.
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For reviews on the synthesis of naturally occurring, axially chiral biaryls, see:
For the electrochemical synthesis of 2,2′-dihydroxy- and 4,4′-dihydroxybiphenyls, see:
Representative examples: