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Conformational Panorama and Chirality Controlled Structure–Energy Relationship in a Chiral Carboxylic Acid Dimer
Author(s) -
Xie Fan,
Seifert Nathan A.,
Jäger Wolfgang,
Xu Yunjie
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202005685
Subject(s) - conformational isomerism , dimer , chirality (physics) , chemistry , enantiomer , ab initio , ab initio quantum chemistry methods , axial chirality , stereochemistry , ring (chemistry) , computational chemistry , crystallography , physics , molecule , chiral symmetry breaking , enantioselective synthesis , organic chemistry , quantum mechanics , symmetry breaking , nambu–jona lasinio model , catalysis
Chirality recognition in dimers of tetrahydro‐2‐furoic acid (THFA) was studied in a conformer‐specific manner using rotational spectroscopy and theoretical approaches. THFA shows a strong preference for the trans ‐ over the cis ‐COOH configuration. Two drastically different scenarios are possible for the detectable (THFA) 2 : a kinetically preferred dimer bound by feeble interactions between two trans THFAs or a thermodynamically favored dimer with a double hydrogen‐bonded ring structure between two cis subunits. To identify the conformers responsible for the extremely dense rotational spectra observed, it was essential not only to locate several hundred homo/heterochiral (THFA) 2 minima in ab initio calculations but also to evaluate the energetic connectivities among the minima. The study further reveals an interesting chirality dependent structure–energy ordering relationship. A method for enantiomeric excess ( ee ) determination of THFA is presented using a recently proposed chiral self‐tag approach.