Highly Enantioselective Catalytic Asymmetric [2+2] Cycloadditions of Cyclic [alpha]-Alkylidene [beta]-Oxo Imides with Ynamides

Highly enantioselective catalytic asymmetric [2+2] cycloadditions of cyclic [alpha]-alkylidene [beta]-oxo imides with ynamides are described. The high reactivity of the cyclic [alpha]-alkylidene [beta]-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 [alpha]-alkylidene [beta]-oxo imide coordinates with CuII through the two imide carbonyls. The imide group in the product can be transformed to amide, nitrile, and ester groups; moreover, it is removable.