| Title: | "DFT Calculations of (1)H NMR Chemical Shifts of Geometric Isomers of Conjugated Linolenic Acids, Hexadecatrienyl Pheromones, and Model Triene-Containing Compounds: Structures in Solution and Revision of NMR Assignments" |
| Author(s): | Venianakis T; Oikonomaki C; Siskos MG; Primikyri A; Gerothanassis IP; |
| Address: | "Section of Organic Chemistry and Biochemistry, Department of Chemistry, University of Ioannina, GR-45110 Ioannina, Greece" |
| DOI: | 10.3390/molecules26113477 |
| ISSN/ISBN: | 1420-3049 (Electronic) 1420-3049 (Linking) |
| Abstract: | "A DFT study of the (1)H NMR chemical shifts, delta((1)H), of geometric isomers of 18:3 conjugated linolenic acids (CLnAs), hexadecatrienyl pheromones, and model triene-containing compounds is presented, using standard functionals (B3LYP and PBE0) as well as corrections for dispersion interactions (B3LYP-D3, APFD, M06-2X and omegaB97XD). The results are compared with literature experimental delta((1)H) data in solution. The closely spaced 'inside' olefinic protons are significantly more deshielded due to short-range through-space H(...)H steric interactions and appear close to or even beyond delta-values of aromatic systems. Several regularities of the computational delta((1)H) of the olefinic protons of the conjugated double bonds are reproduced very accurately for the lowest-energy DFT-optimized single conformer for all functionals used and are in very good agreement with experimental delta((1)H) in solution. Examples are provided of literature studies in which experimental resonance assignments deviate significantly from DFT predictions and, thus, should be revised. We conclude that DFT calculations of (1)H chemical shifts of trienyl compounds are powerful tools (i) for the accurate prediction of delta((1)H) even with less demanding functionals and basis sets; (ii) for the unequivocal identification of geometric isomerism of conjugated trienyl systems that occur in nature; (iii) for tackling complex problems of experimental resonance assignments due to extensive signal overlap; and (iv) for structure elucidation in solution" |
| Keywords: | CLnAs Dft Giao Nmr chemical shifts hexadecatrienyl pheromones; |
| Notes: | "PubMed-not-MEDLINEVenianakis, Themistoklis Oikonomaki, Christina Siskos, Michael G Primikyri, Alexandra Gerothanassis, Ioannis P eng 2050/Hellenic Foundation for Research and Innovation/ Switzerland 2021/07/03 Molecules. 2021 Jun 7; 26(11):3477. doi: 10.3390/molecules26113477" |
