Details

Autor(en) / Beteiligte

• Xie, Fan
• Seifert, Nathan A.
• Jäger, Wolfgang
• Xu, Yunjie

Titel

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

Ist Teil von

• Angewandte Chemie (International ed.), 2020-09, Vol.59 (36), p.15703-15710

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2020

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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. Rotational spectra of tetrahydro‐2‐furoic acid dimers reveal that simple considerations of thermodynamic or kinetic control are insufficient to rationalize the abundances of the observed dimers. Instead, understanding the energetic interconnectivity of the dimeric network driven in part by chirality is required to unravel the mysteries. A novel chiral self‐tag approach for ee determination is tested.