Chemistry of unique chiral olefins. 4. Theoretical studies of the racemization mechanism of trans- and cis-1,1 ',2,2 ',3,3 ',4,4 '-octahydro-4,4 '-biphenanthrylidenes

The minimum energy conformations and racemization barriers for the chiral s terically overcrowded helical alkenes, trans- and cis-1,1',2,2',3,3',4,4'-o ctahydro-4,4'-biphenanthrylidenes (1 and 2), are reported. The trans-1 and cis-2 isomers can each adapt three different conformations, (Pg) and (M,M) (an enantiomeric pair) and an achiral (P,M) meso form, of which only the ch iral isomers were obtained by synthesis. The conformations and heats of for mation of (M,M)-(E)-1, (P,M)-(E)-1, (M,M)-(Z)-2, and (P,M)-(Z)-2 isomers we re determined by MOPAC AM1 calculations. The racemization process for both the trans- and cis- isomers is postulated to occur via the (P,M) isomers by two successive inversions of the cyclohexenyl ring; (M,M) - (P,M) <-> (P,P ). The (M,M) --> (P,M) and reverse (P,M) --> (M,M) isomerizations were simu lated by reaction path calculations, providing the molecular structure and the activation energy of the transition state for each isomerization. For e ach racemization process, the activation enthalpy (Delta H double dagger) w as calculated as 23.9 and 19.9 kcal mol(-1) for trans-olefin 1 and cis-olef in 2, respectively. These values reasonably agree with the experimental val ues obtained by temperature-dependent circular dichroism, optical rotation, and H-1 NMR magnetization transfer measurements: Delta H double dagger = 2 4.6 and 20.8 kcal mol(-1) for trans-olefin 1 and cis-olefin 2, respectively . While the racemization of cis-isomer 2 is controlled by the steric intera ction of H5 with C4'a and C4'b, the surprisingly high barrier for trans-ole fin 1 is due to the severe steric interaction between H5 and H3'alpha and/o r H3'beta protons.