Electron-Withdrawing Trifluoromethyl Groups in Combination
with Hydrogen Bonds in Polyols: Brønsted Acids, Hydrogen-Bond
Catalysts, and Anion Receptors
posted on 2013-06-26, 00:00authored byAlireza Shokri, Xue-Bin Wang, Steven R. Kass
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.