Alkoxy- and amidocarbonylation of functionalised aryl and heteroaryl halides catalysed by a Bedford palladacycle and dppf: a comparison with the primary Pd(ii) precursors (PhCN)2PdCl2 and Pd(OAc)2

Dalton Transactions Pub Date: 2007-01-16 DOI: 10.1039/B615874A

Abstract

The versatility of a Bedford-type palladacycle 1, namely [{Pd(μ-Cl){κ2-P,C-P(OC6H2-2,4-tBu2)(OC6H3-2,4-tBu2)2}}2], as a primary Pd source, in combination with the ligand bis-1,1′-(diphenylphosphino)ferrocene (dppf) has been established in carbonylation reactions of aryl and heteroaryl bromides with methanol, piperidine and related nucleophiles. Palladacycle 1 has been compared with other primary Pd sources, e.g. (PhCN)2PdCl2 and Pd(OAc)2. The efficacy of the carbonylation processes appear to be linked to the [Pd] concentration, substrate : catalyst ratio, CO pressure and reaction temperature. In amidocarbonylation, double carbonylation is observed for certain organohalides. In the case of 2,5-dibromopyridine, regioselective amination (Hartwig–Buchwald type) also occurs as a side-reaction.

Graphical abstract: Alkoxy- and amidocarbonylation of functionalised aryl and heteroaryl halides catalysed by a Bedford palladacycle and dppf: a comparison with the primary Pd(ii) precursors (PhCN)2PdCl2 and Pd(OAc)2
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