Highly enantioselective catalytic asymmetric [2+2] cycloadditions of cyclic α-alkylidene β-oxo imides with ynamides are described. The high reactivity of the cyclic α-alkylidene β-oxo imide allows the [2+2] cycloadditions of a hindered substrate with unreactive ynamides at low temperature. The X-ray crystallographic analysis of the product suggests that the enantioselectivity of the [2+2] cycloaddition can be well explained by the chelate model comprising the intramolecular hydrogen bond, wherein the cyclic α-alkylidene β-oxo imide coordinates with Cu(II) through the two imide carbonyls. The imide group in the product can be transformed to amide, nitrile, and ester groups; moreover, it is removable.

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The asymmetric [2 + 2] cycloaddition of cyclic α‐alkylidene β‐oxo imides (I), (IV), and (VI) with ynamides (II) is reported.