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Role of silver salts in palladium-catalyzed arene and heteroarene C-H functionalization reactions

journal contribution
posted on 2023-05-19, 03:10 authored by Lotz, MD, Camasso, NM, Allan CantyAllan Canty, Sanford, MS
Silver carboxylate salts are widely used as additives in palladium-catalyzed C–H functionalization reactions. However, the role of these silver additives is often not fully understood. This paper describes an investigation of the role of AgOPiv in the stoichiometric activation of C6F5H at a well-defined PdII complex as well as in the PdII-catalyzed oxidative dimerization of 2-alkylthiophenes. Both in situ NMR spectroscopy and H/D exchange studies of the reactions of C6F5H implicate a role for AgOPiv in the C–H cleavage event, generating Ag–C6F5 as an intermediate. The catalytic studies show similar trends despite the different conditions and substrates, suggesting that AgOPiv promotes a similar metalation of the thiophene in the catalytic transformations. This proposal is supported by DFT calculations, which show energetically feasible pathways for concerted metalation–deprotonation of both 2-methylthiophene and pentafluorobenzene at [Ag(OPiv)]2. These studies suggest that initial metalation of C–H substrates at AgI carboxylates should be considered as a plausible pathway in C–H functionalization reactions involving mixtures of Ag and Pd salts.

History

Publication title

Organometallics

Volume

36

Pagination

165-171

ISSN

0276-7333

Department/School

School of Natural Sciences

Publisher

Amer Chemical Soc

Place of publication

1155 16Th St, Nw, Washington, USA, Dc, 20036

Rights statement

Copyright 2016 American Chemical Society

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  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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