New cinchona‐based primary amine catalysts were prepared and screened as organocatalysts for the γ‐alkylation of α,β‐unsaturated aldehydes with bis(4‐dimethylaminophenyl)methanol. Catalyst C3 containing acetic acid group yielded γ‐alkylated products in good yields (up to 94 %) with up to 90 % ee. This new primary aminocatalyst provide new opportunities to explore novel asymmetric transformations.

The direct oxidative α‐alkoxylation of carbonyl compounds is very important, highly desirable but relatively rare. A general and convenient approach has been developed to prepare 3‐oxy‐4‐isochromanones by copper‐catalyzed α‐C(sp3)−H alkoxylation of 4‐isochromanones with alcohols. The key features are easily available starting materials, mild reaction conditions, broad substrate scope, and excellent regioselectivity.