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Benzhydryl Ethers of Tartaric Acid Derivatives: Stereochemical Response of a Dynamically Chiral Propeller
Author(s) -
Grajewski Jakub,
Mądry Tomasz,
Kwit Marcin,
Warżajtis Beata,
Rychlewska Urszula,
Gawroński Jacek
Publication year - 2017
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201700332
Subject(s) - stereocenter , chemistry , intramolecular force , chromophore , hydrogen bond , circular dichroism , chirality (physics) , tartaric acid , cotton effect , ether , stereochemistry , crystallography , molecule , photochemistry , organic chemistry , enantioselective synthesis , nambu–jona lasinio model , physics , quantum mechanics , quark , citric acid , catalysis , chiral symmetry breaking
Abstract The benzhydryl (diphenylmethyl) group is a molecular propeller that can act as a chirality reporter if it is introduced nearby a stereogenic center by making an ether bond. The hydrophobic character of the benzhydryl group allows transformation of insoluble natural tartaric acid derivatives into soluble entities in a nonpolar environment. Electronic circular dichroism spectra, recorded within the short‐wavelength region of the phenyl 1 B transitions (190–200 nm) shows strong bisignate Cotton effects. The signs and magnitudes of these Cotton effects are a function of absolute configuration and conformation of the molecule and do not primarily arise from exciton coupling of chiral benzhydryl chromophores. In crystals, the main‐chain conformation is stabilized by intramolecular hydrogen bonds and CH–CO dipolar interactions. The number of the donor NH groups has a pronounced effect on the preferred conformations and inclusion properties of benzhydryl‐( R , R )‐tartaric acid diamides. Evidence is shown for the solvent dependency of the conformations of NH amides of tartaric acid diphenylmethyl ethers.