CHEMISTRY OF UNIQUE CHIRAL OLEFINS .1. SYNTHESIS, ENANTIORESOLUTION, CIRCULAR-DICHROISM, AND THEORETICAL DETERMINATION OF THE ABSOLUTE STEREOCHEMISTRY OF ',2,2',3,3',4,4'-OCTAHYDRO-4,4'-BIPHENANTHRYLIDENE AND ',2,2',3,3',4,4'-OCTAHYDRO-4,4'-BIPHENANTHRYLIDENE

Unique chiral olefins, ',2,2',3,3',4,4'-octahydro-4,4'-biphenanthrylid ene (1) and its (Z)-isomer 2, were synthesized. When these compounds a re directly enantioresolved by using the HPLC Okamoto column with a ch iral stationary phase, optically pure enantiomers were obtained. The C D spectra of these chiral olefins exhibit very intense Cotton effects in the B-1(b) transition region, reflecting their strongly twisted ct- electron systems. The CD and UV spectra of chiral olefins (M,M)-(E)-1 and (MM)-(Z)-2 were theoretically calculated by the pi-electron self-c onsistent field/configuration interaction/dipole velocity molecular or bital method. From the calculation results, the absolute stereostructu res of these chiral olefins were theoretically determined to be [CD(+) 239.0]-(M,M)-(E)-1 and [CD(+)238.1]-(M,M)-(2)-2, respectively.