Catalytic Double [2 + 2] Cycloaddition Relay Enabled C-C Triple Bond Cleavage of Yne-Allenones.

An unusual catalytic double [2 + 2] cycloaddition relay reaction of yne-allenones with unactivated alkenes and alkynes has been achieved, which enabled C-C triple-bond cleavage to access more than 60 examples of functionalized phenanthren-9-ols with generally good yields. This reaction provides a regioselective and practical method for the construction of carbocyclic ring systems with a high degree of functional group compatibility. Aside from surveying the scope of this transformation, mechanistic details of this process are provided by conducting systematic theoretical calculations.