Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 28924193.
- Also identified by DOI 10.1038/s41467-017-00672-8 and PMC identifier 5603523.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
The reluctance of gold to achieve oxidative addition reaction is considered as an intrinsic limitation for the development of gold-catalyzed cross-coupling reactions with simple and ubiquitous aryl halide electrophiles. Here, we report the rational construction of a Au(I)/Au(III) catalytic cycle involving a sequence of Csp<sup>2</sup>-X oxidative addition, Csp<sup>2</sup>-H auration and reductive elimination, allowing a gold-catalyzed direct arylation of arenes with aryl halides. Key to this discovery is the use of Me-Dalphos, a simple ancillary (P,N) ligand, that allows the bottleneck oxidative addition of aryl iodides and bromides to readily proceed under mild conditions. The hemilabile character of the amino group plays a crucial role in this transformation, as substantiated by density functional theory calculations.Catalysis involving Au(I)/Au(III) cycles are notoriously hampered by the reluctance of Au(I) towards oxidative addition. Here, the authors show that an hemilabile bidentate ligand promotes oxidative addition of aryl halides to Au(I) and the catalytic formation of biaryl coupling products.