{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Wang Y"],"funding":["NIGMS NIH HHS"],"pagination":["3470"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC4119785"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["5"],"pubmed_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."],"journal":["Nature communications"],"pubmed_title":["A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes."],"pmcid":["PMC4119785"],"funding_grant_id":["R01 GM084254"],"pubmed_authors":["Li Y","Cao Z","Zhang L","Wang Y","Wu G","Wang Z"],"additional_accession":[]},"is_claimable":false,"name":"A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes.","description":"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.","dates":{"release":"2014-01-01T00:00:00Z","publication":"2014 Apr","modification":"2025-04-19T04:16:54.43Z","creation":"2019-03-27T01:33:17Z"},"accession":"S-EPMC4119785","cross_references":{"pubmed":["24704803"],"doi":["10.1038/ncomms4470"]}}