Conformational, configurational, and supramolecular studies of podocephalol acetate from Lasianthaea aurea

• Published in: Chirality (New York, N.Y.) Vol. 31; no. 11; pp. 923 - 933
• Main Authors: Rodríguez‐García, Gabriela, Villagómez‐Guzmán, Ana K., Talavera‐Alemán, Armando, Cruz‐Corona, Rosalba, Gómez‐Hurtado, Mario A., Cerda‐García‐Rojas, Carlos M., Joseph‐Nathan, Pedro, Río, Rosa E.
• Format: Journal Article
• Language: English
• Published: United States Wiley Subscription Services, Inc 01.11.2019
• Subjects: Absolute configuration; Acetates - chemistry; Acetic acid; ar‐himachalene; Asteraceae; Asteraceae - chemistry; Circular dichroism; Configurations; Density functional theory; Dichroism; Essential oils; Lasianthaea; Mathematical analysis; Models, Molecular; Molecular Conformation; Molecular structure; NMR; Nuclear magnetic resonance; Physical characteristics; Physical properties; podocephalol; Single crystals; Stereoisomerism; supramolecular analysis; TEM analysis; Terpenes; Transmission electron microscopy; vibrational circular dichroism; podocephalol; TEM analysis; Lasianthaea; Asteraceae; vibrational circular dichroism; supramolecular analysis; absolute configuration; ar-himachalene
• ISSN: 0899-0042; 1520-636X
• DOI: 10.1002/chir.23042

Although podocephalol (1) and its derived acetate 2 were found in Lasianthaea podocephala four decades ago, and 1 was later detected in the essential oils of several vegetal species, its absolute configuration (AC) and conformational preferences remained to be established. The structures of ar‐himachalene 1, now isolated from Lasianthaea aurea, and its derived acetate 2, were herein confirmed by extensive 1D and 2D nuclear magnetic resonance (NMR) studies, while the conformational preferences of the cycloheptene was established by density functional theory (DFT) calculations, which in combination with vibrational circular dichroism measurements provided the (R) absolute configuration of the molecules. The structure and AC were further verified through the Flack and Hooft parameters calculations derived from single crystal X‐ray diffraction data of 2. In addition, careful evaluation of the crystal data allowed observing supramolecular layers cell package, an uncommon property in natural terpenes that might have potential applications. A transmission electron microscopy analysis of crystal of 2 was also possible, providing its physical characteristics at the micrometric scale.