Ruthenium-Catalyzed Asymmetric Allylic Substitution with Metal Carboxylates

Significance

Transition-metal-catalyzed allylic substitution with oxygen nucleophiles is an efficient method for synthesizing optically active allylic alcohols and their derivatives. However, most examples are limited to the synthesis of allylic ethers. Only a few reports are available on asymmetric allylic substitution with carboxylates, probably due to the high reactivity of the resulting allylic esters with metal catalysts. The authors reported a highly efficient ruthenium-catalyzed asymmetric allylic substitution of cinnamyl chloride 2 with sodium carboxylate 3. Excellent regioselectivity and enantioselectivity were obtained using the catalyst (S)-1.