Issue 45, 2020

Oxidative addition of activated aryl-carboxylates to Pd(0): divergent reactivity dependant on temperature and structure

Abstract

With the exception of activated sulfonate esters, oxidative addition of Ar–O bonds to Pd(0) complexes is extremely rare. This has led to a general perception that Pd-catalyzed cross-coupling is not feasible with O-based electrophiles such as aryl esters. We report that pyrone and coumarin esters do undergo oxidative addition to Pd(PCy3)2, with Pd insertion into either the acyl–O or Ar–O bond. Addition of the acyl–O bond to Pd(0) is kinetically favoured and reversible, while addition of the Ar–O bond is thermodynamically favoured. Using a larger and more electron-rich pivalate derivative disfavours acyl–O cleavage, enabling selective oxidative addition of the Ar–O bond and corresponding catalytic cross-coupling.

Graphical abstract: Oxidative addition of activated aryl-carboxylates to Pd(0): divergent reactivity dependant on temperature and structure

Supplementary files

Article information

Article type
Communication
Submitted
24 mar 2020
Accepted
15 apr 2020
First published
15 apr 2020

Dalton Trans., 2020,49, 16067-16071

Oxidative addition of activated aryl-carboxylates to Pd(0): divergent reactivity dependant on temperature and structure

J. Becica, G. Gaube, W. A. Sabbers and D. C. Leitch, Dalton Trans., 2020, 49, 16067 DOI: 10.1039/D0DT01119C

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