Ruthenium-catalyzed cyclopropanation of alkenes using propargylic carboxylates as precursors of vinylcarbenoids.
Intermolecular cyclopropanation reactions of various alkenes with propargylic carboxylates 1 are catalyzed by [RuCl2(CO)3]2 to give vinylcyclopropanes 2 in good yields. The key intermediate of the reaction is a vinylcarbene complex generated in situ by nucleophilic attack of a carbonyl oxygen of the carboxylates to an internal carbon of the alkyne activated by the ruthenium complex. A variety of transition-metal compounds other than the Ru compound can also be employed in this system. Similar cyclopropanation proceeds with conjugated dienes as well to give trans-vic-divinylcyclopropane derivatives and cycloheptadiene derivatives 5, the latter being thermally derived from the initially formed cis-vic-isomers via Cope-type rearrangement. The present reaction is chemically equivalent to the transition metal-catalyzed cyclopropanation reaction using alpha-diazoketones as carbenoid precursors.
Miki
Koji
K
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
Ohe
Kouichi
K
Uemura
Sakae
S