Ruthenium-Catalyzed Cyclopropanation of Alkenes Using Propargylic Carboxylates as Precursors of Vinylcarbenoids
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- 1 October 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (22) , 8505-8513
- https://doi.org/10.1021/jo034841a
Abstract
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 α-diazoketones as carbenoid precursors.Keywords
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