Determination of the Absolute Configurations of Natural Products via Density Functional Theory Calculations of Vibrational Circular Dichroism, Electronic Circular Dichroism and Optical Rotation: The Schizozygane Alkaloid Schizozygine

Citations Over TimeTop 10% of 2007 papers

Abstract

The development of density functional theory (DFT) methods for the calculation of vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and transparent spectral region optical rotation (OR) has revolutionized the determination of the absolute configurations (ACs) of chiral molecules using these chiroptical properties. We report the first concerted application of DFT calculations of VCD, ECD, and OR to the determination of the AC of a natural product whose AC was previously undetermined. The natural product is the alkaloid schizozygine, isolated from Schizozygia caffaeoides. Comparison of DFT calculations of the VCD, ECD, and OR of schizozygine to experimental data leads, for each chiroptical technique, to the AC 2R,7S,20S,21S for the naturally occurring (+)-schizozygine. Three other alkaloids, schizogaline, schizogamine, and 6,7-dehydro-19beta-hydroxyschizozygine, have also been isolated from S. caffaeoides and shown to have structures closely related to schizozygine. Assuming a common biosynthetic pathway, their ACs are defined by that of schizozygine.

Related Papers

• → Assignment of the Absolute Configuration of Concentricolide – Absolute Configuration Determination of Its Bioactive Analogs Using DFT Methods(2009)37 cited
• → Product of alaptide synthesis: Determination of the absolute configuration(2010)16 cited
• → Synthesis and absolute configuration of 3‐ethyl and 3‐n‐propylpyrrolidine(1980)22 cited
• → Comparative Evaluation of Vibrational Circular Dichroism and Optical Rotation for Determination of Enantiomeric Purity(2001)11 cited
• → Absolute configuration assignment of (3‐phenyloxirane‐2,2‐diyl)bis(phenylmethanone) via density functional calculations of optical rotation and vibrational circular dichroism(2010)6 cited