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Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups
Author(s) -
Zoric Marija R.,
Singh Varun,
Zeller Matthias,
Glusac Ksenija D.
Publication year - 2019
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3975
Subject(s) - conformational isomerism , chemistry , intermolecular force , nuclear magnetic resonance spectroscopy , crystallography , linker , density functional theory , stereochemistry , biphenyl , alcohol , molecule , computational chemistry , organic chemistry , computer science , operating system
Conformational flexibility of three covalently linked alcohol dimers, composed of xanthenol units and diphenyl ether (DPE(OH) 2 ), 9,9‐dimethylxanthene (XAN(OH) 2 ), or biphenyl (BP(OH) 2 ) linkers was studied. The relative orientation of the two alcohol units ( In‐In , In‐Out , and Out‐Out conformers) in the model compounds was investigated using NMR spectroscopy, X‐ray crystallography, and density functional theory (DFT) calculations. Diols containing rigid linkers, such as XAN(OH) 2 and BP(OH) 2 , favor the formation of an In‐In conformer in solution, and the interconversion between different conformers was slow on the NMR timescale. Interestingly, XAN(OH) 2 adopted an In‐Out conformation in the crystalline solid state, possibly due to additional intermolecular interactions. More flexible DPE(OH) 2 was found to freely interconvert on the NMR timescale. This study provides important structural information that can be utilized in catalysis, metal‐ligation, and other applications.