Synthesis of chiral auxiliary and multi-activation ligand having phosphonylated sugar moiety and their application for asymmetric synthesis

具有膦酰化糖部分的手性辅助和多活化配体的合成及其在不对称合成中的应用

• 批准号: 14550823
• 负责人: IWAO Yamamoto
• 金额: $ 2.3万
• 依托单位: Shinshu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550823/
• 关键词: chiral auxiliary; Diels-Alder reaction; phosphonylated sugar; asymmetric synthesis; phosphenium cation; 不斉補助基; ジアステレオ選択的

Reaction of methyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside with two equivalents of diphenylphosphenium cation at 0° C gave the α-and β-1-phosphonylated 2-enopyranosides as major products. Similarly, Reaction of diphenylphosphenium cation with tri-O-acetylglycal afforded the same products in a similar ratio. By contrast, a reaction with tri-O-benzylglucal at reflux temperature of dichloromethane afforded the 3-phosphonylated sugar as a major product. These reactions would proceed via stable allyl cations. Furthermore, the 3-phosphonylated sugar was useful for chiral auxiliary. For example, Diels-Alder reaction of an acrylate ester of the 3-phosphonylated sugar with eyclopentadiene gave a cycloadduct in good yield with excellent diastereoselectiviry.

甲基4，6-二-O-乙酰基-2，3-二脱氧-D-赤式-己-2-烯吡喃糖苷与2当量二苯基膦阳离子在0° C下反应，主要产物为α-和β-1-膦酰化的2-烯吡喃糖苷。类似地，二苯基膦阳离子与三-O-乙酰基糖的反应以类似的比例得到相同的产物。相比之下，在二氯甲烷的回流温度下与三-O-苄基葡糖醛的反应得到作为主要产物的3-膦酰化糖。这些反应将通过稳定的烯丙基阳离子进行。此外，3-膦酰化糖是有用的手性辅助。例如，3-膦酰化糖的丙烯酸酯与环戊二烯的狄尔斯-阿尔德反应以良好的产率得到具有优异的非对映选择性的环加合物。

项目成果

I.Yamamoto, T.Fujimoto et al.: "Regioselective Synthesis of Phosphonylated Sugars from Reactions of Glycals with Diphenylphosphenium Cation"J.Carbohydr.Chem.. 22(6). 443-457 (2003)

I.Yamamoto、T.Fujimoto 等人：“从糖醛与二苯基膦阳离子反应中区域选择性合成磷酸化糖”J.CarboHydr.Chem.. 22(6)。

I.Yarnarnoto, T.Fujimoto他: "Regioselective Synthesis of Phosphonylated Sugars from Reactions of Glycals with Diphenylphosphenium Cation"J.Carbohydr.Chem.. 22・6. 443-457 (2003)

I.Yarnarnoto、T.Fujimoto 等：“通过糖醛与二苯基膦阳离子的反应进行磷酸化糖的区域选择性合成”J.CarboHydr.Chem.. 22・6 (2003)。

I.Yamamoto, T.Fujimoto他: "Regioselective Synthesis of Phosphonylated Sugars from Reactions of Glycals with Diphenylphosphenium Cation"J.Carbohydr.Chem.. 22・6. 443-457 (2003)

I. Yamamoto、T. Fujimoto 等：“通过二苯基膦阳离子的反应进行磷酸化糖的区域选择性合成” J. Chem. 22・6 (2003)。