Steroselective Intramolecular Cyclization Using Palladium Catalyst and Its Application to the Synthesis of Natsural Products

钯催化剂立体选择性分子内环化及其在天然产物合成中的应用

• 批准号: 10640514
• 负责人: HIRAI Yoshiro
• 金额: $ 2.11万
• 依托单位: Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640514/
• 关键词: stereoselective cyclization; palladium (II) catalyst; silver trifluoroacetate; trans(2,6)piperidine; trans(2,4)piperidine; (+)-prosopinine; (-)-SS20846A; (+)-Deoxymannojirimycin; パラジウム錯体; 消化管運動抑制作用; (S)-glycidol; 1-deoxymannojirimycin; グリコシダーゼ

The intramolecular cyclization of the optically active urethanes containing allylic alkohol was effected by treatment with bis(acetonitrile)palladium (II) chloride to give the trans(2,6)piperidine system as a single diastereoisomer. During these transformations, the Pd (II) species are not reduced and thus the catalyst can recycle without its reoxidation. On the other hand, cyclization of the simillar substrate containing allylic chloride using silver trifluoroacetate in the presence of sodium hydride afforded the cis(2,6)piperidine system. Cyclization of other substrates using these transition metal complexes was also examined and simillar results were obtained.The cyclo-adducts obtained were proved to be useful chiral building blocks by their conversion into (+)-prosopinine, (-)-SS20846A, (+)-Deoxymannojirimycin, and (-)-hydroxysedamine, respectively

通过用双(乙腈)氯化钯(II)处理来实现含有烯丙基醇的光学活性氨基甲酸酯的分子内环化，得到作为单一非对映异构体的反式(2,6)哌啶系统。在这些转化过程中，Pd (II) 物质不会被还原，因此催化剂可以循环利用而无需再氧化。另一方面，在氢化钠存在下，使用三氟乙酸银环化含有烯丙基氯的类似底物，得到顺式(2,6)哌啶系统。还检查了使用这些过渡金属配合物对其他底物的环化，并获得了类似的结果。通过将所得环加合物分别转化为(+)-前沙品宁、(-)-SS20846A、(+)-脱氧甘露尻霉素和(-)-羟基床胺，证明它们是有用的手性结构单元

项目成果

Hajime Yokoyama: "Asymmetric Synthesis of Chiral 2-Fluorinated 1,3-propan propanciol and Its Application to the Preparation of Monofluorinated Chiral synfhon"Tetrahedron Letters. 39. 7741-7744 (1998)

Hajime Yokoyama：“手性2-氟化1,3-丙醇的不对称合成及其在单氟化手性合成物制备中的应用”四面体字母。

平井美朗: "2価のパラジウム触媒を用いる含窒素ヘテロ理の離伝い選択的な構築と天然物不斉合成への応用"有機合成化学協会誌. 56. 34-44 (1988)

Yoshiro Hirai：“使用二价钯催化剂选择性构建含氮异源性及其在天然产物不对称合成中的应用”有机合成化学学会杂志 56. 34-44 (1988)。

Hajime Yokoyama: "Total Synthesis of SS20846A via Intramolecular Pd(II)-catalyzed Cyclization"Tetrahedron Letters. 39. 5971-5974 (1998)

Hajime Yokoyama：“通过分子内 Pd(II) 催化环化全合成 SS20846A”四面体字母。

Hajime Yokoyama, Kumiko Otaya, Seiji Yamaguchi, and Yoshiro Hirai: "Total Synthesis of SS20846A via Intramolecular Pd(II)-catalyzed Cyclization"Tetrahedron Letters. 39. 5971-5974 (1998)

Hajime Yokoyama、Kumiko Otaya、Seiji Yamaguchi 和 Yoshiro Hirai：“通过分子内 Pd(II) 催化环化全合成 SS20846A”四面体字母。

Yoshiro Hirai 他3名: "Total Synthesis of SS20846A uia Intromolecutar Pc(CII)-catalyzed cyclization" TETRAHEDRON LETTERS. 39・33. 5971-5974 (1998)

Yoshiro Hirai 等 3 人：“SS20846A uia Intromolecutar Pc(CII) 催化环化的全合成”TETRAHEDRON LETTERS 39・33 (1998)。