The synthesis of tricyclo[5.2.1.01 234'10]deca-2,5,8-triene (1), 1,10-dimethyltricyclo[5.2.1.04,1°]deca-2,5,8-triene (3), and tetracyclo[5.5.2.01,8.04,8]tetradeca-2,5,13-triene (4) has been accomplished via the reaction of 1,2-dicarbonyl compounds with di-zerz-butyl 3-oxoglutarate (Weiss reaction). Condensation of glyoxal 5a with di-rerZ-butyl 3-oxoglutarate (6b) gave the tetra-te/7-butyl w-dioxobicyclo[3.3.0]octane-2,4,6,8-tetracarboxylate 7b in 93% yield. This bisenol 7b was converted into the bisenol ether 9b regios pecifically (90% yield). This transformation was followed by monoalkylation (KH, allyl iodide; -58 °C) and hydrolysis to generate 2-allyl-n4-bicyclo[3.3.0]octane-3,7-dione in 90% overall yield from 9b. The mixture of epimeric 2-allyl-3,7-diones 11a,b was transformed (03; DMS) into the mixture of epimeric aldehydes 12a,b. This process was followed by aldol cyclization (2 N HC1, THF) to provide the diastereomeric mixture of endo-(13a) and exo-(13b) triquinane monols in 85% yield. Reduction of 13a,b with borane-THF (0 °C) generated the stereoisomeric mixture of triols 14a,b which were subjected to an HMPA-mediated dehydration sequence to provide triquinacene (1), accompanied by small amounts of isotriquinacene. The mixture of trienes were converted into pure 1 by exposure to p-TSA in methylene chloride-pentane. Substitution of biacetyl (5b) for glyoxal 5a in the Weiss reaction, followed by the analogous steps detailed in the synthesis of 1, provided 1,10-dimethyltriquinacene (3). In addition, the synthesis of 1,10-cyclohexanotriquinacene (4), another centro-substituted triquinacene, has been accomplished by substitution of cyclohexane-1,2-dione (23) for 5a in the condensation, followed by the same sequence of reactions presented above for 1 and 3.