Chemoenzymatic Approach to Optically Active 4-Hydroxy-5-alkylcyclopent-2-en-1-one Derivatives: An Application of a Combined Circular Dichroism Spectroscopy and DFT Calculations to Assignment of Absolute Configuration

• Published in: Chirality (New York, N.Y.) Vol. 26; no. 6; pp. 300 - 306
• Main Authors: Frelek, Jadwiga, Karchier, Michał, Madej, Daria, Michalak, Karol, Różański, Paweł, Wicha, Jerzy
• Format: Journal Article
• Language: English
• Published: United States Blackwell Publishing Ltd 01-06-2014; Wiley Subscription Services, Inc
• Subjects: Candida - enzymology; Candida antarctica lipase; chiral cyclopentenones; Chirality; Circular Dichroism; Circularity; Cyclopentanes - chemistry; density functional theory; Derivatives; Dichroism; electronic circular dichroism; Hydrogen-Ion Concentration; kinetic resolution; Kinetics; Lipase - chemistry; Magnetic Resonance Spectroscopy; Mathematical analysis; Models, Molecular; Models, Statistical; Molecular Conformation; Optical activity; Piancatelli rearrangement; Spectra; Spectrophotometry, Infrared; Spectrophotometry, Ultraviolet; Spectroscopy; Stereoisomerism; vibrational circular dichroism; Piancatelli rearrangement; chiral cyclopentenones; density functional theory; vibrational circular dichroism; kinetic resolution; electronic circular dichroism; Candida antarctica lipase
• ISSN: 0899-0042; 1520-636X
• DOI: 10.1002/chir.22322

ABSTRACTA series of representative optically active derivatives of 4‐hydroxy‐5‐alkylcyclopent‐2‐en‐1‐one were prepared from the respective 2‐furyl methyl carbinols via the Piancatelli rearrangement followed by the enzymatic kinetic resolution of racemates. Applicability of chiroptical methods (experimental and calculated electronic circular dichroism [ECD] and vibrational circular dichroism [VCD] spectra) to determine the absolute configuration of both stereogenic centers in 4‐hydroxy‐5‐methylcyclopent‐2‐en‐1‐one was demonstrated. It was also demonstrated that the concurrent application of ECD and VCD spectroscopy can be used for the determination of the configuration of two stereogenic centers. Chirality 26:300–306, 2014. © 2014 Wiley Periodicals, Inc.