Synthesis of the Carbocyclic Core of Massadine.

The carbocyclic core of massadine has been synthesized relying on a stereoselective formal [3 + 2] cycloaddition of lithiumtrimethylsilyldiazomethane with α,β-unsaturated esters to form a Δ(2)-pyrazoline moiety followed by facile N-N bond cleavage. A unique feature of the current approach is the direct installation of the tertiary α-amino center and a β-cyano group in a cis arrangement on the resulting cyclopentane framework via a previously developed formal aminocyanation protocol.