title: Electron-withdrawing trifluoromethyl groups in combination with hydrogen bonds in polyols: Brønsted acids, hydrogen-bond catalysts, and anion receptors.
abstract: Electron-withdrawing trifluoromethyl groups were characterized in combination with hydrogen-bond interactions in three polyols (i.e., CF3CH(OH)CH2CH(OH)CF3, 1; (CF3)2C(OH)C(OH)(CF3)2, 2; ((CF3)2C(OH)CH2)2CHOH, 3) by pKa measurements in DMSO and H2O, negative ion photoelectron spectroscopy and binding constant determinations with Cl(-). Their catalytic behavior in several reactions were also examined and compared to a Brønsted acid (HOAc) and a commonly employed thiourea ((3,5-(CF3)2C6H3NH)2CS). The combination of inductive stabilization and hydrogen bonds was found to afford potent acids which are effective catalysts. It also appears that hydrogen bonds can transmit the inductive effect over distance even in an aqueous environment, and this has far reaching implications.
authors.affiliation: Department of Chemistry, University of Minnesota, 207 Pleasant St SE, Minneapolis, Minnesota 55455, United States.
authors.forename: Alireza
authors.initials: A
authors.lastname: Shokri
authors.forename: Xue-Bin
authors.initials: XB
authors.lastname: Wang
authors.forename: Steven R
authors.initials: SR
authors.lastname: Kass
mesh_terms: D000143:Acids / Q000737:chemistry*; D000438:Alcohols / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D002384:Catalysis; D004583:Electrons; D006860:Hydrogen Bonding; D015394:Molecular Structure
chemical_list: D000143:Acids; D000438:Alcohols; D000838:Anions