Tailored Quinones Support High-turnover Pd Catalysts for Oxidative C-H Arylation with O

Overview

Journal Science

Specialty Science

Date 2020 Nov 20

PMID 33214286

Citations 13

Authors

Chase A Salazar

Kaylin N Flesch

Brandon E Haines

Philip S Zhou

Djamaladdin G Musaev

Shannon S Stahl

Affiliations

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Abstract

Palladium(II)-catalyzed carbon-hydrogen (C-H) oxidation reactions could streamline the synthesis of pharmaceuticals, agrochemicals, and other complex organic molecules. Existing methods, however, commonly exhibit poor catalyst performance with high palladium (Pd) loading (e.g., 10 mole %) and a need for (super)stoichiometric quantities of undesirable oxidants, such as benzoquinone and silver(I) salts. The present study probes the mechanism of a representative Pd-catalyzed oxidative C-H arylation reaction and elucidates mechanistic features that undermine catalyst performance, including substrate-consuming side reactions and sequestration of the catalyst as an inactive species. Systematic tuning of the quinone cocatalyst overcomes these deleterious features. Use of 2,5-di--butyl--benzoquinone enables efficient use of molecular oxygen as the oxidant, high reaction yields, and >1900 turnovers by the Pd catalyst.

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