Molecular Orbital Studies on Pericyclic Reactions of Cinnamyl Xanthates in β-Cyclodextrin Cavities

Masashi ETO; Shoji KUBOTA; Hidetoshi NAKAGAWA; Yasuyuki YOSHITAKE; Kazunobu HARANO

doi:10.1248/cpb.48.1652

Masashi ETO, Shoji KUBOTA, Hidetoshi NAKAGAWA, Yasuyuki YOSHITAKE, Kazunobu HARANO

著者情報

キーワード: O-cinnamyl S-methyl dithiocarbonate, β-cyclodextrin, pericyclic reaction, S-(1-phenylallyl) S-methyl dithiocarbonate, PM3, asymmetric induction

ジャーナルフリー

2000 年 48 巻 11 号 p. 1652-1659

DOI https://doi.org/10.1248/cpb.48.1652

詳細

抄録

The solid β-cyclodextrin (β-CyD) complex of O-cinnamyl S-methyl dithiocarbonates (xanthate, 1a), upon heating at 45°C, underwent asymmetric [3, 3]-sigmatropic rearrangement to give the optically S-(1-phenylallyl) S-methyl dithiocarbonate (2a) with 60% ee. Heating the β-CyD complex of 2a at 120°C caused extrusion of COS to give cinnamyl methyl sulfide (3a) in high yield. The reaction behavior and role of β-CyD are discussed based on molecular orbital calculation data.

責任著者(Corresponding author)

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