Rhodium(I)-catalyzed intramolecular ene reaction of vinylidenecyclopropanes and alkenes for the formation of bicyclo[5.1.0]octylenes.
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.
Li
Wei
W
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, PR China.
Yuan
Wei
W
Shi
Min
M
Hernandez
Erik
E
Li
Guigen
G
D000475:Alkenes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D003516:Cycloparaffins / Q000138:chemical synthesis* / Q000737:chemistry; D003903:Deuterium / Q000737:chemistry; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*
D000475:Alkenes; D001643:Bridged Bicyclo Compounds; D003516:Cycloparaffins; D003903:Deuterium; D012238:Rhodium