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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Fluorine in fragrances: exploring the difluoromethylene (CF2) group as a conformational constraint in macrocyclic musk lactones

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Corr, Michael J. [1] ; Cormanich, Rodrigo A. [2] ; von Hahmann, Cortney N. [1] ; Buehl, Michael [1] ; Cordes, David B. [1] ; Slawin, Alexandra M. Z. [1] ; O'Hagan, David [1]
Total Authors: 7
[1] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife - Scotland
[2] Univ Estadual Campinas, Dept Chem, BR-13083970 Campinas, SP - Brazil
Total Affiliations: 2
Document type: Journal article
Source: ORGANIC & BIOMOLECULAR CHEMISTRY; v. 14, n. 1, p. 211-219, 2016.
Web of Science Citations: 7

The CF2 group is incorporated into specific positions within the lactone ring of the natural musk lactone, (12R)-(+)-12-methyl-13-tridecanolide, a constituent of Angelica root oil, Angelica archangelica L. The approach is taken as it was anticipated that CF2 groups would dictate corner locations in the macrocycle and limit the conformational space available to the lactone. Three fluorine containing lactones are prepared by organic synthesis. One (8) has CF2 groups located at the C-6 and C-9 positions, another (9) with CF2 groups at the C-5 and C-9 positions, and a third (10) with a CF2 group at C-8. Two of the fluorine containing lactones (8 and 10) were sufficiently crystalline to obtain X-ray crystal structures which revealed that the CF2 groups do adopt corner locations. All three lactones were subject to computational analysis at the B3LYP-D3/6-311+G{*}{*} level to assess the relative energies of different conformers. In all cases, the global minima and most of the lowest energy minima have squared/rectangular geometries and located the CF2 groups at the corners. The lowest energy structures for 8 and 10 closely approximated the observed X-ray structures, suggesting good convergence of theory and experiment in determining relevant low energy conformations. All three compounds retained a pleasant odour suggesting the rings retained sufficient conformational flexibility to access relevant olfactory conformations. (AU)

FAPESP's process: 15/00975-7 - Synthesis of bioactive compounds and studies of relative stereochemistry by hydrogen nuclear magnetic resonance (1H NMR)
Grantee:Rodrigo Antonio Cormanich
Support type: Scholarships in Brazil - Post-Doctorate