Salicylates, 3-aryl-3,4-dihydroisocoumarins and sterically encumbered and functionalized biaryls were synthesized using 1,3-bis(silyl enol ethers) by TiCl4-mediated regioselective [3+3] cyclocondensation strategy. While functionalized fluoranthenes, 4-aryl-1-bromo-2-trifluoromethylbenzenes, 2,5-diaryl-1-trifluoromethylbenzene and terphenyls and tetraaryl-p-benzoquinones were synthesized by palladium(0)-catalyzed Heck and Suzuki cross coupling reactions.