Abstract: | The rhodium‐catalyzed asymmetric cycloisomerization of heteroatom‐bridged 1,6‐ene‐ynamides proceeded to give high yields of functionalized 3‐aza‐ and oxabicyclo[4.1.0]heptene derivatives with high enantioselectivity, which was achieved by use of a rhodium/chiral diene catalyst. The 1,6‐ene‐ynamides substituted with 2‐oxazolidinone and 2‐azetidinone moieties at the alkyne terminus were found to display high reactivity towards the rhodium/chiral diene catalyst, where the chelate coordination of the alkyne moiety and the carbonyl oxygen of the ene‐ynamides might be responsible for the high catalytic activity. |