title: Development of Novel Cyclizations via Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry.
abstract: Novel Rh(I)-catalyzed cyclizations through a different type of rhodacycle intermediate which is formed by hydroacylation of 4,6-dienal or oxidative addition of diene and alkene are described. Hydroacylation of 4,6-dienal afforded various 7-membered rings in good to high yields, while cycloisomerization of diene and alkene provided 5- or 6-membered rings in good yields. On the basis of these studies, we have also succeeded in developing the sequential reaction of hydroacylation followed by cycloisomerization to produce bicyclic compounds in a stereoselective manner and thus this reaction was expanded to the synthesis of epiglobulol. Furthermore, both Rh(I)-catalyzed hydroacylation and cycloisomerization using ionic liquid (IL) as a solvent were investigated and it was found that the IL recovered after the reaction, which contains the Rh(I) catalyst, could be recycled several times without loss of catalytic activity.
authors.affiliation: Faculty of Pharmaceutical Sciences, Hokkaido University.
authors.forename: Yoshihiro
authors.initials: Y
authors.lastname: Oonishi
mesh_terms: D000215:Acylation; D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D003500:Cyclization; D006844:Hydrocarbons, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D007536:Isomerism; D010084:Oxidation-Reduction; D012238:Rhodium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D001643:Bridged Bicyclo Compounds; D006844:Hydrocarbons, Cyclic; D012238:Rhodium