For CP-capped diene-ynes 1b-1f with R 1 =Ar group, the [4+2+1] products 2b-2f were obtained in moderate to good yields, ranging from 67% to 82% (Table ). Among them, a longer reaction time (48 hours) was essential to have a full conversion of 1d bearing an electron-withdrawing CF3 group on the aryl ring of its R 1 group (Table , entry 4). To our delight, the desired [4+2+1] cycloadduct can be generated at an elevated temperature of 80 °C when a methyl-terminated CPcapped diene-yne 1g was employed as the substrate (Table ). Substrates 1h-1j containing alkene substituents in the alkyne moiety of CP-capped diene-ynes also gave corresponding products in moderate to excellent yields (from 60% to 97%, Table , entries 8-10). In this case, substrates 1i and 1j had lower reactivities (their reaction times were 24 and 48 hours, respectively) and gave moderate yields of 60% and 66%, respectively. In contrast, substrate 1h with a vinyl group produced 2h in 97% yield in 3 hours. We reasoned that the steric effect introduced by the substituent was responsible for the less satisfactory reaction yields for both 1i and 1j compared to that for substrate 1g with a methyl group. We also tested 1k-1m with R 2 or R 3 substituents in the diene moiety of the substrates, finding all of these reactions took place smoothly (Table , entries 11-13). Further studies demonstrated that, both oxygenand carbon-tethered substrates (1n and 1o) can deliver the expected bicyclic 5/7 compounds successfully (Table , entries 14 and 15). The 2π component of the present [4+2+1] reaction can be alkenes, as exemplified by the reaction of 1p, affording 2p in an acceptable yield of 42%, even though the reaction temperature had to be 80 °C ( , Yu 14 , and Wender respectively. Furthermore, vinyl cyclopropane isomerization converted 3c to 3f with a diene group when Wilkinson's catalyst was used. We can envision 3f can be further transformed into many other molecules if the rich chemistry of internal diene can be utilized.