title: Three hydrogen bond donor catalysts: oxyanion hole mimics and transition state analogues.
abstract: Enzymes and their mimics use hydrogen bonds to catalyze chemical transformations. Small-molecule transition state analogues of oxyanion holes have been characterized by computations, gas-phase IR and photoelectron spectroscopy, and determination of their binding constants in acetonitrile. A new class of hydrogen bond catalysts is proposed (donors that can contribute three hydrogen bonds to a single functional group) and demonstrated in a Friedel-Crafts reaction. The employed catalyst was observed to react 100 times faster than its rotamer that can employ only two hydrogen bonds. The former compound also binds anions more tightly and was found to have a thermodynamic advantage.
authors.affiliation: Department of Chemistry, University of Minnesota, Minneapolis, 55455, United States.
authors.forename: Evgeny V
authors.initials: EV
authors.lastname: Beletskiy
authors.forename: Jacob
authors.initials: J
authors.lastname: Schmidt
authors.forename: Xue-Bin
authors.initials: XB
authors.lastname: Wang
authors.forename: Steven R
authors.initials: SR
authors.lastname: Kass
mesh_terms: D000097:Acetonitriles / Q000138:chemical synthesis / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D002384:Catalysis; D006860:Hydrogen Bonding; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000097:Acetonitriles; D000838:Anions; D010100:Oxygen