THE COMPLICATED CONFORMATIONAL LANDSCAPES OF TETRAHYDRO-2-FUROIC DIMER AND MONOHYDRATE: BROADBAND ROTATIONAL SPECTRA AND COMPREHENSIVE CONFORMATIONAL SEARCHES

Xie, Fan

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https://hdl.handle.net/2142/104555 Copy

Description

Title

THE COMPLICATED CONFORMATIONAL LANDSCAPES OF TETRAHYDRO-2-FUROIC DIMER AND MONOHYDRATE: BROADBAND ROTATIONAL SPECTRA AND COMPREHENSIVE CONFORMATIONAL SEARCHES

Author(s)

Xie, Fan

Contributor(s)

Xu, Yunjie ; Jäger, Wolfgang ; Heger, Matthias ; Seifert, Nathan A.

Issue Date

2019-06-19

Keyword(s)

Mini-symposium: Non-covalent Interactions

Abstract

Tetrahydro-2-furoic acid (THFA), a chiral carboxylic acid which is often used as a precursor in syntheses of pharmaceuticals, exhibits a complex conformational landscape in its monomeric form.1 Detailed analyses of its conformational distribution and conversion barriers using rotational spectroscopy and theoretical modeling were reported recently.1 In the current study, we focus on investigated how intermolecular interactions with water and THFA itself influence the aforementioned conformational preference. A large number of initial conformational geometries were generated using a semiempirical tight-binding (TB) quantum chemistry code, GFN-xTB, designed for prediction of equilibrium structural properties, such as geometries, vibrational frequencies, and non-covalent interactions.2 The final geometry optimizations were carried out at the B3LYP-D3(BJ)/def2-TZVP, B3LYP-D3(BJ)/6-311++G(2d,p), and MP2/6-311G++(2d,p) levels of theory. Very interestingly, in the THFA monohydrate, the two monohydrates observed contain the most stable THFA monomeric conformer and are ranked the ninth and tenth in terms of their relative energy ordering. On the other hand, the THFA dimer observed contains the third most stable monomeric conformers. We interpret the observed phenomena in terms of the conformational conversion barriers and conformational cooling effects.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/104555

DOI

10.15278/isms.2019.WB03

Copyright and License Information

Copyright 2019 Fan Xie

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