MOLECULAR ASYMMETRY .8. TRANS-BICYCLO[8.2.2]TETRADECA-5,10,12,13-TETRAENE

fran.s-Bicyclo[8.2.2]tetradeca-5,10,12,13-tetraene (1) has been synthesized by reduction of trans-bicyclo-[8.2.2]tetradeca-5,10,12,13-tetraene-4,7-dione (2) with an excess of lithium aluminum hydride and aluminum chloride in a 1: 3 ratio. Platinum complexes of the olefin 1 containing optically active α-methylbenzylamine were prepared. Fractional crystallization to constant rotation of the complex containing (R)-(+)-α-methylbenzylamine afforded (–)-trans-dichloro(trans-bicyclo[8.2.2.]tetradeca-5,10,12,13-tetraene)(α-methylbenzylamine)platinum(II) (4a), [α]25D –35.1°. Fractional crystallization of the enantiomeric complex containing (S)-(–)-α-methylbenzyl-amine gave complex 4b, [α]25D +37.7°. Decomposition of partially resolved complex 4a with aqueous sodium cyanide at room temperature afforded optically inactive olefin 1. This observation suggests that the molecule is undergoing spontaneous racemization at this temperature. © 1968, American Chemical Society. All rights reserved.