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Nat Commun. 2014 Apr 7;5:3470. doi: 10.1038/ncomms4470.

A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes.

Author information

1
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
2
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Ling Ling Road 345, Shanghai 200032, China.

Abstract

Most homogenous gold catalyses demand ≥ 0.5 mol% catalyst loading. Owing to the high cost of gold, these reactions are unlikely to be applicable in medium- or large-scale applications. Here we disclose a novel ligand design based on the privileged (1,1'-biphenyl)-2-ylphosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3'-position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogenous gold catalysis considering the spatial challenge of using ligand to reach anti-approaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalysing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding.

PMID:
24704803
PMCID:
PMC4119785
DOI:
10.1038/ncomms4470
[Indexed for MEDLINE]
Free PMC Article

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