Electron-withdrawing trifluoromethyl groups in combination with hydrogen bonds in polyols: Brønsted acids, hydrogen-bond catalysts, and anion receptors

Alireza Shokri; Xue Bin Wang; Steven R. Kass

doi:10.1021/ja4036384

Electron-withdrawing trifluoromethyl groups in combination with hydrogen bonds in polyols: Brønsted acids, hydrogen-bond catalysts, and anion receptors

Alireza Shokri, Xue Bin Wang, Steven R. Kass

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Abstract

Electron-withdrawing trifluoromethyl groups were characterized in combination with hydrogen-bond interactions in three polyols (i.e., CF ₃CH(OH)CH₂CH(OH)CF₃, 1; (CF₃) ₂C(OH)C(OH)(CF₃)₂, 2; ((CF₃) ₂C(OH)CH₂)₂CHOH, 3) by pK_a 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-(CF ₃)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.

Original language	English (US)
Pages (from-to)	9525-9530
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	135
Issue number	25
DOIs	https://doi.org/10.1021/ja4036384
State	Published - Jun 26 2013

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title = "Electron-withdrawing trifluoromethyl groups in combination with hydrogen bonds in polyols: Br{\o}nsted 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., CF 3CH(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 Br{\o}nsted acid (HOAc) and a commonly employed thiourea ((3,5-(CF 3)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.",

author = "Alireza Shokri and Wang, {Xue Bin} and Kass, {Steven R.}",

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T1 - Electron-withdrawing trifluoromethyl groups in combination with hydrogen bonds in polyols

T2 - Brønsted acids, hydrogen-bond catalysts, and anion receptors

AU - Shokri, Alireza

AU - Wang, Xue Bin

AU - Kass, Steven R.

PY - 2013/6/26

Y1 - 2013/6/26

N2 - Electron-withdrawing trifluoromethyl groups were characterized in combination with hydrogen-bond interactions in three polyols (i.e., CF 3CH(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-(CF 3)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.

AB - Electron-withdrawing trifluoromethyl groups were characterized in combination with hydrogen-bond interactions in three polyols (i.e., CF 3CH(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-(CF 3)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.

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Electron-withdrawing trifluoromethyl groups in combination with hydrogen bonds in polyols: Brønsted acids, hydrogen-bond catalysts, and anion receptors

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