title: Molecular orbital studies on pericyclic reactions of cinnamyl xanthates in beta-cyclodextrin cavities.
abstract: The solid beta-cyclodextrin (beta-CyD) complex of O-cinnamyl S-methyl dithiocarbonates (xanthate, 1a), upon heating at 45 degrees C, underwent asymmetric [3,31-sigmatropic rearrangement to give the optically S-(1-phenylallyl) S-methyl dithiocarbonate (2a) with 60% ee. Heating the beta-CyD complex of 2a at 120 degrees C caused extrusion of COS to give cinnamyl methyl sulfide (3a) in high yield. The reaction behavior and role of beta-CyD are discussed based on molecular orbital calculation data.
authors.affiliation: Faculty of Pharmaceutical Sciences, Kumamoto University, Japan.
authors.forename: M
authors.initials: M
authors.lastname: Eto
authors.forename: S
authors.initials: S
authors.lastname: Kubota
authors.forename: H
authors.initials: H
authors.lastname: Nakagawa
authors.forename: Y
authors.initials: Y
authors.lastname: Yoshitake
authors.forename: K
authors.initials: K
authors.lastname: Harano
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D002934:Cinnamates / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003505:Cyclodextrins / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D013871:Thiones / Q000737:chemistry*; D047392:beta-Cyclodextrins
chemical_list: D002934:Cinnamates; D003505:Cyclodextrins; D013871:Thiones; D047392:beta-Cyclodextrins; C031215:betadex