Effect of Hydrogen Bonds on pKa Values: Importance of Networking
作者： Alireza Shokri , Azardokht Abedin , Alireza Fattahi , Steven R Kass , None
DOI: 10.1021/JA3037349
关键词: Acetic acid 、 Enzyme catalysis 、 Hydrogen bond 、 Oxygen 、 Alcohol 、 Low-barrier hydrogen bond 、 Chemistry 、 Medicinal chemistry 、 Base (chemistry) 、 Inorganic chemistry 、 Solvation
摘要: The pKa of an acyclic aliphatic heptaol ((HOCH2CH2CH(OH)CH2)3COH) was measured in DMSO, and its gas-phase acidity is reported as well. This tertiary alcohol found to be 1021 times more acidic than tert-butyl DMSO order magnitude acetic acid (i.e., = 11.4 vs 12.3). can attributed a 21.9 kcal mol–1 stabilization the charged oxygen center conjugate base by three hydrogen bonds another 6.3 resulting from additional between uncharged primary secondary hydroxyl groups. Charge delocalization both first second solvation shells may used facilitate enzymatic reactions. Acidity constants series polyols were also computed, combination hydrogen-bonding electron-withdrawing substituents afford acids that are predicted extremely < 0). These bond enhanced represent attractive class Bronsted ...
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