Catalytic Enantioselective [10+4] Cycloadditions.

The first peri- and stereoselective [10+4] cycloaddition between catalytically generated amino isobenzofulvenes and electron-deficient dienes is described. The highly stereoselective catalytic [10+4] cycloaddition exhibits a broad scope with high yields, reflecting a robust higher-order cycloaddition. Experimental and computational investigations support a kinetic distribution of intermediate rotamers dictating the enantioselectivity, which relies heavily on additive effects.