TY - JOUR
T1 - Vibrational Circular Dichroism Study of Pipitzols and of Their Inverse Epimer Constituents α- and β-Pipitzol
AU - Burgueño-Tapia, Eleuterio
AU - Fernández, Mónica Díaz
AU - Joseph-Nathan, Pedro
N1 - Publisher Copyright:
© The Author(s) 2022.
PY - 2022/9
Y1 - 2022/9
N2 - Inverse epimers are uncommon in nature and a lack of study of their vibrational circular dichroism (VCD) behavior seems evident. This is relevant, among other facts, since in the case of epimers, VCD has been capable of determining the absolute configuration (AC) of 1 stereogenic center in a molecule having 10 stereogenic centers. The case of pipitzol is unique since it took 80 years from its first preparation by thermal intramolecular cycloaddition of perezone (1) to know that the reaction outcome is an equimolar mixture of the 2 inverse epimers α-pipitzol (2: 3R, 3aR, 7R, and 8aS) and β-pipitzol (3: 3R, 3aS, 7S, and 8aR). Evaluation of 2 and 3 reveals that some VCD bands have an opposite phase while other bands show the same phase. The VCD spectrum of the naturally occurring equimolecular mixture was also measured and the 3 experimental spectra were contrasted with density functional theory (DFT) calculated spectra allowing individual band assignments. The comparisons were made in the 1800 to 950 and 1550 to 950 cm−1 ranges and the numerical differences are highlighted thereby showing that carbonyl bands influence such comparisons. The 2 carbonyl absorption bands of 2 and 3 show weak VCD bands and the conjugated double bond band provides an intense AC-dependent VCD band.
AB - Inverse epimers are uncommon in nature and a lack of study of their vibrational circular dichroism (VCD) behavior seems evident. This is relevant, among other facts, since in the case of epimers, VCD has been capable of determining the absolute configuration (AC) of 1 stereogenic center in a molecule having 10 stereogenic centers. The case of pipitzol is unique since it took 80 years from its first preparation by thermal intramolecular cycloaddition of perezone (1) to know that the reaction outcome is an equimolar mixture of the 2 inverse epimers α-pipitzol (2: 3R, 3aR, 7R, and 8aS) and β-pipitzol (3: 3R, 3aS, 7S, and 8aR). Evaluation of 2 and 3 reveals that some VCD bands have an opposite phase while other bands show the same phase. The VCD spectrum of the naturally occurring equimolecular mixture was also measured and the 3 experimental spectra were contrasted with density functional theory (DFT) calculated spectra allowing individual band assignments. The comparisons were made in the 1800 to 950 and 1550 to 950 cm−1 ranges and the numerical differences are highlighted thereby showing that carbonyl bands influence such comparisons. The 2 carbonyl absorption bands of 2 and 3 show weak VCD bands and the conjugated double bond band provides an intense AC-dependent VCD band.
KW - cedranolides
KW - inverse epimers
KW - inverse-epimeric pairs
KW - sesquiterpenoids
KW - vibrational circular dichroism
UR - http://www.scopus.com/inward/record.url?scp=85139116760&partnerID=8YFLogxK
U2 - 10.1177/1934578X221127970
DO - 10.1177/1934578X221127970
M3 - Artículo
AN - SCOPUS:85139116760
SN - 1934-578X
VL - 17
JO - Natural Product Communications
JF - Natural Product Communications
IS - 9
ER -