Chiraloptical properties of adducts derived from cyclic nitrones and 2( 5H)-furanones. Combined experimental and theoretical studies

Abstract

The validity of the Bucourt–Legrand empirical rule, which relates the configuration at the α-carbon atom in the lactone unit with the sign of the lactone n→π ∗ transition observed in the electronic circular dichroism (ECD) spectrum of 5-5-5 and 5-5-6 fused heterocyclic systems, was investigated. For this purpose, a combination of ECD spectroscopy, time-dependent density functional theory (TD-DFT) and molecular modelling calculations supported additionally by X-ray diffraction analysis, was applied. Model compounds were obtained via the 1,3-dipolar cycloaddition of 2( 5H)-furanones and five- and six-membered cyclic nitrones. In addition, cycloadducts either with or without an additional interfering chromophore were selected. A comparison of the recorded ECD spectra with those simulated by the TD-DFT calculations gave a reasonable interpretation of the excitations observed in the 210–230 nm spectroscopic range. Generally, calculations confirmed the validity of the Bucourt–Legrand rule and demonstrated that ECD may be used as a highly sensitive probe for the three-dimensional molecular structure of the systems studied herein. Notable behaviour, however, was observed in the case of some 5-5-6 fused systems substituted with BnO group. In these cases, the conformational liability and coupling of molecular lactone excitation with other chromophores cause a change of orientation of the transition dipole moments resulting in a breakdown of the rule.