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Synlett 2013; 24(19): 2519-2524
DOI: 10.1055/s-0033-1339545
DOI: 10.1055/s-0033-1339545
cluster
Is the Isodesmic Reaction Approach a Better Model for Accurate Calculation of pK a of Organic Superbases? A Computational Study
Further Information
Publication History
Received: 16 July 2013
Accepted: 18 July 2013
Publication Date:
27 August 2013 (online)
Abstract
The acid-base dissociation constant (pK a) can be related to the solubility and binding of drugs. However, measuring accurate pK a values is a challenging task. In this study, we have examined the pK a of various organic superbases: naphthalenes, cyclic guanidines, vinamidines, and acyclic guanidines computationally. We have calculated the pK a of such superbases by employing two methods: a conventional thermodynamic cycle and a second method based on an isodesmic reaction. The thermodynamic cycle involves computation of solvation free energy by using gas-phase free energy and the difference in solvation free energies (∆Gsolv) between products and reactants. Calculations performed with the isodesmic reaction approach do not use the free energy of solvation; hence, the accuracy of the approach is less sensitive to solvent molecules and global charges of the calculated species. The root-mean-square errors (RMSE) predict that the pK a of the studied organic superbases are more accurate when calculated with the isodesmic reaction approach.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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