We have successfully using the exocyclic double bond of tricarbonyliron triene complexes to undergo (2+1) and (4+2) cycloaddition for the rapid construction of spiro[2.5]octane and spiro[5.5]undecane system. These cycloaddition reactions were chemo-, regio-, and stereoselective. Synthetic studies toward Upenamide, Manzamine A and Manzamine J by using 1-cyano-2,4-cyclohexadiene tricarbonyliron complexes were also discussed.