Conformational Panorama and Chirality Controlled Structure-Energy Relationship in a Chiral Carboxylic Acid Dimer - PubMed (original) (raw)

. 2020 Sep 1;59(36):15703-15710.

doi: 10.1002/anie.202005685. Epub 2020 Jul 9.

Affiliations

• PMID: 32500551
• DOI: 10.1002/anie.202005685

Conformational Panorama and Chirality Controlled Structure-Energy Relationship in a Chiral Carboxylic Acid Dimer

Fan Xie et al. Angew Chem Int Ed Engl. 2020.

Abstract

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.

Keywords: carboxylic acids; chirality; conformation analysis; dimers; rotational spectroscopy.

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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