Chemistry of Unique Chiral Olefins. 1. Synthesis, Enantioresolution, Circular Dichroism, and Theoretical Determination of the Absolute Stereochemistry of trans- and cis-1,1´,2,2´,3,3´,4,4´-Octahydro-4,4´-biphenanthrylidenes

摘要

Unique chiral olefins, (E)-1,1´,2,2´,3,3´,4,4´-octahydro-4,4´-biphenanthrylidene (1) and its (Z)-isomer 2, were synthesized. When these compounds are directly enantioresolved by using the HPLC Okamoto column with a chiral stationary phase, optically pure enantiomers were obtained. The CD spectra of these chiral olefins exhibit very intense Cotton effects in the 1Bb transition region reflecting their strongly twisted π-electron systems. The CD and UV spectra of chiral olefins (M,M)-(E)-1 and (M,M)-(Z)-2 were theoretically calculated by the π-electron self-consistent field/configuration interaction/dipole velocity molecular orbital method. From the calculation results, the absolute stereostructures of these chiral olefins were theoretically determined to be [CD(+)239.0]-(M,M)-(E)-1 and [CD(+)238.1]-(M,M)-(Z)-2, respectively.