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Synthesis 2019; 51(16): 3060-3076
DOI: 10.1055/s-0037-1611482
paper
© Georg Thieme Verlag Stuttgart · New York

Access to Biphenyls by Palladium-Catalyzed Oxidative Coupling of Phenyl Carbamates and Phenols

Nadina Truchan
,
Christian Jandl
,
Alexander Pöthig
,
Stefan Breitenlechner
,
Thorsten Bach  *
Department Chemie and Catalysis Research Center (CRC), Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany   eMail: thorsten.bach@ch.tum.de
› Institutsangaben
This project was supported by the Deutsche Forschungsgemeinschaft (Ba 1372-19/1) and by the Graduate School, Technische Universität München.
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Publikationsverlauf

Received: 14. März 2019

Accepted: 19. März 2019

Publikationsdatum:
15. April 2019 (online)

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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.

Key words

biaryls - carbamates - C-H activation - cross-coupling - oxidation - Pd catalysis.

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 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.

  • Primary Data
 

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