The efficient asymmetric preparation of the C2-symmetric annulated cyclopentadienes, (+)-(1R,7R,8R,10R)-8, 10-diisopropyltricyclo[5.2.2.02,6]undeca-2,5-diene (1) and (-)-(1S,7S,8R,10R)-8,10-dimethyltricyclo [5.2.2.02,6]undeca-2,5-diene(2) is described. The key step in these syntheses is an asymmetric dihydroboration of 1,4-dialkyl-1,4-cyclohexadienes using enantiomerically pure isopinocamphenylborane. The overall yield of enantiomerically enriched 1 or 2 is 27% and 20%, respectively, for the five-step synthesis (Birch reduction of 1,4-dialkylbenzene, asymmetric dihydroboration-oxidation, bis(methanesulfonate) formation, bisalkylation of cyclopentadiene, and [1,5]-sigmatropic rearrangement). The formation of chiral titanocene dichlorides is described.