A tandem platinum dichloride-catalyzed cycloisomerization and rearrangement reaction of enynes leads to the formation of 2,4-pentadienals, 1-aryl-tetrahydro-1H-indenes, or 3-methylene-4-vinylcyclohex-1-enes; depending upon the substituent(s) and tether group of the enynes, the platinum dichloride-catalyzed cycloisomerization products, bicyclo-hept-2-enes, undergo a Claisen rearrangement, a 1,5-hydrogen shift, or a vinylcyclopropane rearrangement.