Molecular orbital studies on pericyclic reactions of cinnamyl xanthates in beta-cyclodextrin cavities.
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.
Eto
M
M
Faculty of Pharmaceutical Sciences, Kumamoto University, Japan.
Kubota
S
S
Nakagawa
H
H
Yoshitake
Y
Y
Harano
K
K
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
D002934:Cinnamates; D003505:Cyclodextrins; D013871:Thiones; D047392:beta-Cyclodextrins; C031215:betadex