Ruthenium-Catalyzed Allylation of Aromatic Compounds and Allylic Ether Formation

Abstract

Ruthenium-catalyzed allylation of aromatic compounds such as benzene, toluene, p-xylene, anisole, phenol, furans, and thiophenes with allylic alcohol derivatives gives the corresponding allylated products in good to high yields with a high regioselectivity. Only the cationic thiolate-bridged diruthenium(III, III) complexes promote the reaction. Investigation of the allylation pathway in the reaction of cinnamyl alcohol with p-xylene has revealed that it proceeds via two ways: a direct allylation with the alcohol itself and an allylation with dicinnamyl ether formed as an intermediate. A new cationic thiolate-bridged diruthenium(III, IV) complex together with allylated cinnamyl chlorides has been formed in the reaction of the diruthenium(III, III) complex with cinnamyl chloride, this new complex being revealed to be effective as an allylation catalyst. The cationic diruthenium(III, III) complexes can also catalyze the allylation of simple alcohols with allylic alcohols to give the corresponding alkyl ally...