Diols as Dienophiles: Bridged Carbocycles via Ruthenium(0)‐Catalyzed Transfer Hydrogenative Cycloadditions of Cyclohexadiene or Norbornadiene

Highly exo‐selective ruthenium(0) catalyzed transfer hydrogenative cycloadditions of 1,2‐diols with cyclohexadiene or norbornadiene are described. Novel bridged bicyclic ring systems are accessible from the diol, α‐ketol or 1,2‐dione oxidation levels with complete control of diastereoselectivity.     

Catalytic,Enantioselective Synthesis of 1,2‐anti‐Diols by Asymmetric Ring‐Opening/Cross‐Metathesis

An enantioselective method for the synthesis of 1,2‐anti‐diols has been developed. A cyclometalated chiral‐at‐ruthenium complex catalyzes the asymmetric ring‐opening/cross‐metathesis of dioxygenated cyclobutenes, thus resulting in functionally rich synthetic building blocks. Syntheses of the insect pheromone (+)‐endo‐brevicomin and monosaccharide ribose demonstrate the synthetic utility of the 1,2‐anti‐diol fragments generated in the title reaction.