Absolute configuration of verticillane diterpenoids by vibrational circular dichroism.
Good agreement between theoretical and experimental vibrational circular dichroism curves of (1S,11S,12S)-(+)-verticilla-3E,7E-dien-12-ol (1) established the absolute configuration of this natural diterpene isolated from Bursera suntui. Molecular modeling of 1 was carried out using the Monte Carlo protocol followed by geometry optimization at the B3LYP 6-31G(d,p) level of theory. The 12-membered ring of 1 was found in a single preferred chair-chair-chair-chair conformation. In the six-membered ring a chair prevails over a distorted boat, and the C-OH bond rotation generates three predominant rotamers. Validation of the minimum energy conformation for 1 was achieved by comparison of theoretical and experimental infrared frequencies, vicinal 1H NMR coupling constants, and X-ray diffraction data. This study confirms that (+)-verticillol 1 isolated from Bursera species has the 1S,11S,12S absolute configuration that corresponds to the same enantiomeric series as verticillanes from Sciadopitys and Taxus, while verticillanes from Jackiella and Jungermannia have antipodal structures.
Cerda-García-Rojas
Carlos M
CM
Departamento de Química, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, Apartado 14-740, México, DF, 07000 Mexico. ccerda@cinvestav.mx
García-Gutiérrez
Hugo A
HA
Hernandez-Hernandez
Juan D
JD
Roman-Marín
Luisa U
LU
Joseph-Nathan
Pedro
P
D031233:Bursera / Q000737:chemistry*; D002942:Circular Dichroism; D018360:Crystallography, X-Ray; D004224:Diterpenes / Q000737:chemistry* / Q000302:isolation & purification*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism
D004224:Diterpenes