title: Advanced Structural Determination of Diterpene Esters Using Molecular Modeling and NMR Spectroscopy.
abstract: Three new jatrophane esters (1-3) were isolated from Euphorbia amygdaloides ssp. semiperfoliata, including an unprecedented macrocyclic jatrophane ester bearing a hemiketal substructure, named jatrohemiketal (3). The chemical structures of compounds 1-3 and their relative configurations were determined by spectroscopic analysis. The absolute configuration of compound 3 was determined unambiguously through an original strategy combining NMR spectroscopy and molecular modeling. Conformational search calculations were performed for the four possible diastereomers 3a-3d differing in their C-6 and C-9 stereocenters, and the lowest energy conformer was used as input structure for geometry optimization. The prediction of NMR parameters ((1)H and (13)C chemical shifts and (1)H-(1)H coupling constants) by density functional theory (DFT) calculations allowed identifying the most plausible diastereomer. Finally, the stereostructure of 3 was solved by comparison of the structural features obtained by molecular modeling for 3a-3d with NMR-derived data (the values of dihedral angles deduced from the vicinal proton-proton coupling constants ((3)JHH) and interproton distances determined by ROESY). The methodology described herein provides an efficient way to solve or confirm structural elucidation of new macrocyclic diterpene esters, in particular when no crystal structure is available.
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, University Paris-Saclay , 91198, Gif-sur-Yvette, France.|Laboratoire de Chimie des Produits Naturels, UMR CNRS SPE 6134, University of Corsica , 20250, Corte, France.
authors.forename: Louis-Félix
authors.initials: LF
authors.lastname: Nothias-Scaglia
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, University Paris-Saclay , 91198, Gif-sur-Yvette, France.
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Gallard
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, University Paris-Saclay , 91198, Gif-sur-Yvette, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Dumontet
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, University Paris-Saclay , 91198, Gif-sur-Yvette, France.
authors.forename: Fanny
authors.initials: F
authors.lastname: Roussi
authors.affiliation: Laboratoire de Chimie des Produits Naturels, UMR CNRS SPE 6134, University of Corsica , 20250, Corte, France.
authors.forename: Jean
authors.initials: J
authors.lastname: Costa
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, University Paris-Saclay , 91198, Gif-sur-Yvette, France.
authors.forename: Bogdan I
authors.initials: BI
authors.lastname: Iorga
authors.affiliation: Laboratoire de Chimie des Produits Naturels, UMR CNRS SPE 6134, University of Corsica , 20250, Corte, France.
authors.forename: Julien
authors.initials: J
authors.lastname: Paolini
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS, UPR 2301, University Paris-Saclay , 91198, Gif-sur-Yvette, France.
authors.forename: Marc
authors.initials: M
authors.lastname: Litaudon
mesh_terms: D004224:Diterpenes / Q000737:chemistry* / Q000302:isolation & purification*; D004952:Esters; D028481:Euphorbia / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D011522:Protons; D013237:Stereoisomerism
chemical_list: D004224:Diterpenes; D004952:Esters; D011522:Protons; C530345:jatrophane