Article

Rhodium(I)-catalyzed intramolecular ene reaction of vinylidenecyclopropanes and alkenes for the formation of bicyclo[5.1.0]octylenes.

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, PR China.
Organic Letters (Impact Factor: 6.14). 12/2009; 12(1):64-7. DOI: 10.1021/ol902505p
Source: PubMed

ABSTRACT An efficient catalytic system for the intramolecular ene reaction of allene and alkene of diarylvinylidenecyclopropanes has been established. The reaction was achieved by using [RhCl(CO)(2)](2) as the catalyst in co-solvents of toluene and acetonitrile. MeCN was found to play a crucial role in controlling the reaction toward formation of bicyclo[5.1.0]octylene derivatives. An alternative system consisting of [RhCl(CO)(2)](2) and toluene in the absence of MeCN was found to give [2 + 2] cycloaddition adducts. The structures have been unambiguously determined by X-ray structural analysis. Deuterium labeling experiments were conducted to confirm the mechanism hypothesis.

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