title: Overriding the alkynophilicity of gold: catalytic pathways from higher energy Au(I)-substrate complexes and reactant deactivation via unproductive complexation in the gold(I)-catalyzed propargyl Claisen rearrangement.
abstract: Computational and experimental analysis of unusual substituent effects in the Au-catalyzed propargyl Claisen rearrangement revealed new features important for the future development of Au(I) catalysis. Despite the higher stability of Au-alkyne complexes, they do not always correspond to the catalytically active compounds. Instead, the product emanates from the higher energy Au(I)-oxygen complex reacting via a low barrier cation-accelerated oxonia Claisen pathway. Additionally, both intra and intermolecular competition from other Lewis bases present in the system, for the Au(I) catalyst, can lead to unproductive stabilization of the substrate/catalyst complex, explaining hitherto unresolved substituent effects.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA.
authors.forename: Dinesh V
authors.initials: DV
authors.lastname: Vidhani
authors.forename: John W
authors.initials: JW
authors.lastname: Cran
authors.forename: Marie E
authors.initials: ME
authors.lastname: Krafft
authors.forename: Igor V
authors.initials: IV
authors.lastname: Alabugin
mesh_terms: D000466:Alkadienes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D006046:Gold / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D000466:Alkadienes; D000480:Alkynes; D006046:Gold