Steroselective Construction of Nitrogen Hetero-alicycles Using Palladium Catalyst and Its Application to the Synthesis of Natsural Products

钯催化剂立体选择性构建氮杂脂环化合物及其在天然产物合成中的应用

• 批准号: 06672090
• 负责人: HIRAI Yoshiro
• 金额: $ 1.34万
• 依托单位: Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06672090/
• 关键词: stereoselective cyclization; trans (2,6) piperidine; cis (2,6) piperidine; palladium (II) catalyst; silver trifluoroacetate; (+) -prosopinine; (+) -pseudoconhydrine; (+) -palustrine; 2,6-cis-ピペリジン; (+)-palustrine; 分子内付加環化; 有機銀塩; 香月-Sharpless不斉

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 aoso examined and simillar results were obtained.The cyclo-adducts obtained were proved to be useful chiral building blocks by their conversion into (+) -prosopinine, (+) -pseudoconhydrine, and the important synthetic intermediate of (+) -palustrine, respectively

用双（乙腈）氯化钯（II）处理含手性取代基的烯丙基醇进行分子内环化反应，得到反式（2，6）哌啶体系的单一非对映异构体。在这些转化过程中，Pd（II）物质不被还原，因此催化剂可以再循环而无需再氧化。另一方面，在氢化钠存在下，用三氟乙酸银环化含烯丙基氯的类似底物，得到顺式（2，6）哌啶体系。用这些过渡金属配合物对其他底物进行了环化反应，得到了类似的结果，并分别转化为（+）-丙索品宁、（+）-假康尼醇和（+）-沼泽苦素的重要合成中间体，证明了这些环化产物是有用的手性结构单元

项目成果

Yoshiro Hirai and Mayumi Nagatsu: "Construction of Chiral 2-Functionalized Piperidine via Enzymatic Resolution and Palladium-catalyzed N-Alkylation" CEMISTRY LETTERS. 21-22 (1994)

Yoshiro Hirai 和 Mayumi Nagatsu：“通过酶解和钯催化的 N-烷基化构建手性 2-官能化哌啶”CEMISTRY 快报。

Yoshiro Hirai: "Construction of Chiral Piperidine via Enzymatic Resolution and Palkdiam-cotalyzed N-Alkylation" Chsmistry Letters. 21-22 (1994)

Yoshiro Hirai：“通过酶解和 Palkdiam 共催化的 N-烷基化构建手性哌啶”化学快报。

Yoshiro Hirai: "Construction of Chiral 2-Fusod Piperidine via Enzynatic Resolution and Palladium-catalyzed N-Alkylation" Chemistry Letters. 21-22 (1994)

Yoshiro Hirai：“通过酶解和钯催化的 N-烷基化构建手性 2-Fusod 哌啶”化学快报。