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1,2-ジオール分子認識に基づく選択的分子変換反応


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Title: 1,2-ジオール分子認識に基づく選択的分子変換反応
Other Titles: Selective molecular transformation of 1,2-diols based on molecular recognition
Authors: 松村, 功啓 / 尾野村, 治 / 出水, 庸介
Authors (alternative): Matsumura, Yoshihiro / Onomura, Osamu / Demizu, Yosuke
Issue Date: Mar-2007
Publisher: 有機合成化学協会
Citation: 有機合成化学協会誌 65(3) pp.216-225, 2007
Abstract: On the bases of the concept that a coordination of 1,2-diols 1 with an appropriate metal ion(M^n+) might form an activated five-membered intermediate in which the OH group is much activated than those of non-activated 1, we examined a monobenzoylation of 1 by benzoyl chloride using tin and copper ions as M^n+. As the results, the monobenzoylation of 1 was achieved with high selectivity even in the presence of monools. The monobenzoylation reactions were then applied to kinetic resolution of dl-1 and asymmetric desymmetrization of meso-1 using a chiral organotin or BOX(bisoxazoline)-CuCl_2 as a catalyst. In particular, the asymmetric outcome using (R, R)-Ph-BOX-CuCl_2 catalyst was promising and attractive. That is, the kinetic resolution of dl-1(with up to >99.9% ee for monobenzoylation of hydrobenzoin), its application to a synthesis of D-inositol-1-phosphate (100% ee), the asymmetric desymmetrization of meso-1(with up to 94% ee for monobenzoylation of meso-1,2-hydrobenzoin and 93% ee for monocarbamoylation of meso-l,2-cyclooctanediol), and the asymmetric desymmetrization of meso-1,3-diols(with up to 55% ee for the monobenzoylation of ethyl 2-ethyl-2-hydroxymethyl-3-hydroxypropanoate) were achieved. Also, the method was applied to electrochemical oxidation of 1 and its asymmetric version(38% ee for the asymmetric desymmetrization of meso-hydrobenzoin and 72% ee for the kinetic resolution of dl-hydrobenzoin).
Keywords: molecular recognition / 1,2-diols / kinetic resolution / asymmetric desymmetrization / benzoylation / oxidation / electrochemical oxidation
URI: http://hdl.handle.net/10069/16318
ISSN: 00379980
Type: Journal Article
Text Version: publisher
Appears in Collections:Articles in academic journal

Citable URI : http://hdl.handle.net/10069/16318

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