光学活性な6-デオキシ-6, 6, 6-トリフルオロヘキソピラノースの立体選択的合成

概要

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Although 6-deoxy-6, 6, 6-trifluorosugars are considered as possible biologically active materials incorporated into naturally occurring antibiotics, there has been no report even on their preparation when our project has started. Then, the authors have planned to synthesize this class of sugars in an optically pure form via enzymatic optical resolution of furanols with a trifluoromethyl moiety, followed by peracid oxidation leading to 2-butenolides. During our study, this resolution was found to be highly efficient when substrates with trimethylsilyl or <I>t</I>-butyldimethylsilyl moieties in the furan ring were employed, furnishing almost optically pure materials in good yields. It was considered for the first moment that the complicated usage of protective groups would be required for the transformation of the above butenolides or their hydrogenated derivatives, butyrolactones, into the corresponding hexopyranoses with a 6-membered ring structure. However, this problem was solved by the development of the sequential 1, 2-silyl migration-ring expansion, which was novelly deviced by the consideration of the characteristics of lactols. This unique reaction was qualitatively supported by semiempirical molecular orbital calculations by MOPAC (AM 1).
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