Solvation of 2-(hydroxymethyl)-2,5,7,8-tetramethyl-chroman-6-ol revealed by circular dichroism: a case of chromane helicity rule breaking

Physical Chemistry Chemical Physics : PCCP
Joanna E RodeJadwiga Frelek

Abstract

The primary goal of this work is to clarify why 2-(hydroxymethyl)-2,5,7,8-tetramethyl-chroman-6-ol {(S)-TMChM} deviates from the chromane helicity rule under solvent change. The rule, applicable to determining the absolute configuration of molecules containing the chromane chromophore, binds the sign of the 1Lb Cotton effect (CE) with the helicity of the dihydropyran ring. In case of TMChM, however, this CE exhibits extreme solvent dependence: it is negative in non-coordinating solvents and positive in coordinating ones, irrespective of the helicity of the heterocyclic ring. TD-DFT calculations using PCM and hybrid solvation models were performed to explain origin of this phenomenon. It turned out that the 1Lb CE sign directly depends on the position of the phenolic OH group at carbon atom C6 (OHC6). In the absence of interactions with solvents (as in CCl4 or nC6H14) or when a solvent plays proton donor role (as in CHCl3), the OHC6 lies in the phenyl plane and the 1Lb CE sign follows the P/M helicity rule. In contrast, in proton acceptor solvents, like DMSO, CH3OH or CH3CN, the OHC6 group is deflected from the phenyl plane, and the 1Lb CE sign of individual (S)-TMChM conformers depends on the sector in which the OHC6 is located...Continue Reading

References

Feb 13, 2002·International Journal of Pharmaceutics·G AvelloneV Turco Liveri
Feb 20, 2007·Molecular Aspects of Medicine·Roberta RicciarelliCinzia Domenicotti
Jun 13, 2008·Physical Chemistry Chemical Physics : PCCP·Elke DebieBenjamin van der Veken
Jun 19, 2008·Chirality·Francesco MazziniPiero Salvadori
Mar 25, 2010·The Journal of Chemical Physics·Giovanni Scalmani, Michael J Frisch
Jul 1, 2010·Journal of Natural Products·Naoki Iwata, Susumu Kitanaka
Mar 23, 2011·The Journal of Physical Chemistry. B·Kathrin H HopmannPetr Bouř
May 5, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Elke DebiePatrick Bultinck
Jun 28, 2011·Physical Chemistry Chemical Physics : PCCP·Sándor GóbiGyörgy Tarczay
Dec 19, 2012·Physical Chemistry Chemical Physics : PCCP·Mohammad Reza PoopariYunjie Xu
Mar 28, 2013·The Journal of Physical Chemistry. B·Anna PikulskaMagdalena Pecul
Apr 9, 2013·Journal of Natural Medicines·Alfarius Eko Nugroho, Hiroshi Morita
Nov 8, 2013·The Journal of Physical Chemistry. B·Joanna E RodeJoanna Sadlej
Feb 12, 2014·Physical Chemistry Chemical Physics : PCCP·Christian MertenWolfram Sander
Feb 27, 2014·Organic & Biomolecular Chemistry·Marcin GóreckiJadwiga Frelek
Jul 16, 2014·The Journal of Physical Chemistry. B·Louise H FornanderBengt Nordén
Oct 7, 2014·Chirality·Francisco E JorgeRogério N Suave
Jul 1, 2015·Physical Chemistry Chemical Physics : PCCP·François ZielinskiPaul L A Popelier
Dec 27, 2015·Pharmacology & Therapeutics·Hong Yong PehW S Fred Wong
Oct 6, 2016·Journal of Chemical Theory and Computation·Tommaso GiovanniniChiara Cappelli
Jun 1, 2017·Physical Chemistry Chemical Physics : PCCP·Christian Merten
Jun 27, 2017·Physical Chemistry Chemical Physics : PCCP·Karoline Bünnemann, Christian Merten
Nov 7, 2017·Chirality·Marcin GóreckiGennaro Pescitelli
Jan 10, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Daniele Padula, Gennaro Pescitelli

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Citations

Jan 30, 2019·Pharmaceuticals·Marcin GóreckiGennaro Pescitelli

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Methods Mentioned

BETA
circular dichroism

Software Mentioned

Gaussian09
CompareVOA
Conflex

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