Products Cited in Publications Worldwide Initiation of Palladium Precatalysts: Efficiency and Product Selectivity as a Function of Ligand, Substrate, and Reaction Conditions

Initiation of Palladium Precatalysts: Efficiency and Product Selectivity as a Function of Ligand, Substrate, and Reaction Conditions

Wolesensky, Robert M; Morales-Colón, María T; Sanford, Melanie S

DOI:

Abstract

This article describes a detailed interrogation of the initiation step (reduction of PdII to Pd0) for Buchwald’s G3 palladium precatalysts and derivatives thereof. These studies demonstrate that under Suzuki–Miyaura cross-coupling conditions, the cyclometalated PdII complexes initiate to form a mixture of two organic products: carbazole (via intramolecular C(sp2)–N coupling) and biaryl (via intermolecular C(sp2)–C(sp2) coupling with the arylboronic acid substrate). The overall yield and rate of initiation, as well as the organic product ratio, vary dramatically as a function of the phosphine ligand, base, solvent, and boronic acid structure. Implications of these results for catalysis are discussed, and the findings are applied to a different class of cyclometalated precatalysts. Overall, this work shows that precatalyst activation is highly condition-dependent and that this step should be a key consideration in the optimization of Pd-catalyzed cross-coupling reactions.

Keywords

palladium ; precatalyst ; cross-coupling ; ligands ; selectivity ; kinetics

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2-Fluorophenylboronic acid

A2920571993-03-998%

2-Fluorophenylboronic acid

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