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. 2010 Sep 22;132(37):12859-61.
doi: 10.1021/ja106257n.

C-C coupling reactivity of an alkylgold(III) fluoride complex with arylboronic acids

Neal P Mankad  1 , F Dean Toste
Affiliations

C-C coupling reactivity of an alkylgold(III) fluoride complex with arylboronic acids

Neal P Mankad et al. J Am Chem Soc. .

Abstract

Previously, alkylgold(III) fluorides have been proposed as catalytic intermediates that undergo C-C coupling with reagents such as arylboronic acids in Au(I)/Au(III) cross-coupling reactions. Here is reported the first experimental evidence for this elementary mechanistic step. Complexes of the type (NHC)AuMe (NHC = N-heterocyclic carbene) were oxidized with XeF(2) to yield cis-(NHC)AuMeF(2) products, which were found to be in equilibrium with their fluoride-dissociated, dimeric [(NHC)AuMe(μ-F)](2)[F](2) forms. In one case, a monomeric cis-(NHC)AuMeF(2) complex was favored exclusively in solution, and it was found to react with a variety of ArB(OH)(2) reagents to yield Ar-CH(3) products.

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Figures

Figure 1
Figure 1
Au-F region of the 19F NMR spectra of (a) a mixture of 2 and 3, (b) 5, and (c) 9 in CDCl3 solution at room temperature.
Figure 2
Figure 2
Solid-state structure of dicationic 3 (50% probability ellipsoids). Hydrogen atoms and co-crystallized anions and solvent molecules have been omitted for clarity. Selected bond lengths (Å) and angles (°): Au(I)-C(1), 1.968(4) Å; Au(1)-C(28), 2.029(4); Au(1)-F(1), 2.034(3); Au(1)-F(1#), 2.124(3); Au(1)-Au(1#), 3.1789(6); Au(1)-F(1)-Au(1#), 99.69(12).
Scheme 1
Scheme 1
Synthesis of alkylgold(III) fluoride complexes
Scheme 2
Scheme 2
Two possible C-C coupling pathways
See this image and copyright information in PMC

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