Gold Catalyzed Decarboxylative Cross-Coupling of Iodoarenes

Abstract

This report details a decarboxylative cross-coupling of (hetero)aryl carboxylates with iodoarenes in the presence of a gold catalyst (>25 examples, up to 96% yield). Generating an aryl nucleophile via decarboxylation obviates problems associated with transmetalation at a putative gold(III) complex. This reaction is site specific, which overcomes prior limitations associated with gold catalyzed oxidative coupling reactions. The reactivity of the (hetero)aryl carboxylate correlates qualitatively to the field effect parameter (Fortho). Furthermore, each step in a proposed mechanism was observed from isolated gold complexes, supporting a gold catalyzed mechanism. ASSOCIATED CONTENT Supporting InformationThe Supporting Information is available free of charge on the ACS Publications website at DOI: XX. Experimental procedures and data (PDF)

Circular Discovery in Small Molecule and Conjugated Polymer Synthetic Methodology

“…One such example uses stoichiometric Ag in a method of decarboxylative coupling. 73 , 74 Here, a Ag carboxylate is delivered to the Au metal center using Ag(I) to Au(III) transmetalation. Another report, inspired by a Au/Ag dual catalytic system, sought to discover a Pd/Ag system with catalytic amounts of both metals for direct arylation.…”

Stable Au(I) catalysts for oxidant-free C-H functionalization with iodoarenes

“…[15,18,50] 1e). [55] Recently, Shen et al proposed a diaryl gold-catalyzed reaction to form a C(sp 2 )-X cross coupled product, where X is a halide. [55] All together, these recent efforts on oxidative addition to gold(I) have opened new opportunities for gold in cross-coupling reactions.…”

“…[55] Recently, Shen et al proposed a diaryl gold-catalyzed reaction to form a C(sp 2 )-X cross coupled product, where X is a halide. [55] All together, these recent efforts on oxidative addition to gold(I) have opened new opportunities for gold in cross-coupling reactions. The development of catalysts capable of direct arylation without external oxidants is an unmet need in gold-catalysis toward biaryl synthesis.…”

Silver-Mediated Decarboxylation Reactions: Expanding Reaction Scope through Kinetic Analysis

“…Initially, a small set of 22 heteroaromatic carboxylic acids was used to study this transformation. These substrates largely represent the heteroaromatic carboxylic acids known to undergo decarboxylation reactions, [13,18,19,36,43,50,53,87,93,[129][130][131][132][133][134][135][136][137][138][139][140][141] however, this scope of carboxylic acids is incomplete given the desire to develop a model to predict the decarboxylation of a larger scope of heteroaromatic carboxylic acids. Given this, a more exhaustive scope of heteroaromatic acids based on commonly used pharmaceutically relevant cores [151] is proposed in Figure 3-15.…”

“…The construction of the hetero-biaryl motif by decarboxylative coupling reactions have been sparsely reported by a number of groups. [13,18,19,87,93,[129][130][131][132][133][134][135][136][137][138] While many of these reports showcase a wide scope of ortho-functionalized benzoic acids, the reported heteroaromatic carboxylic acid scope is largely limited to a small selection, typically with the heteroatom in the position alpha to the carboxylic acid functionality (Figure 3-2). Intriguingly, a similar scope can be seen for protodecarboxylation reactions of heteroaromatic carboxylic acids.…”