Total Synthesis of (-)-Gephylotoxin 223AB via Asymmetric 1,3-Dipolar Cycloaddition

通过不对称 1,3-偶极环加成法全合成 (-)-Gephylotoxin 223AB

• 批准号: 62570953
• 负责人: KIBAYASHI Chihiro
• 金额: $ 1.22万
• 依托单位: Tokyo College of Pharmacy
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62570953/
• 关键词: Asymmetric 1,3-Dipolar Cycloaddition; Nitrone; (S)-Allyl Ether; Inside Alkoxy Transition State; (-)-Coniine; (+) -モノモリン I; 不斉1,3ー双極子環付加反応; (+)-モノモリン I

Asymmetric 1,3-dipolar cycloaddition of nitrones by using a chiral allyl ether as a dipolarophile and application to an enantioselective synthesis of (-)-coniine and (+)-monomorine I has been investigated. The cyclic and acyclic nitrones were allowed to react with (s)-3-benzyloxy-1-heptene, resulting in the preferential formation (3:1) of the (2R,3aS)-and (3S,5R)-isoxazolidine derivatives, respectively, predicted by application of the inside alkoxy more reactive conformation in a transition state. These cycloadducts were enantiomerically converted to (-)-coniine and (+)-monomorine I,respectively.

研究了使用手性烯丙基醚作为亲偶极试剂进行硝酮的不对称 1,3-偶极环加成反应，并将其应用于 (-)-乌贼碱和 (+)-单芥碱 I 的对映选择性合成。让环状和无环硝酮与(s)-3-苄氧基-1-庚烯反应，导致优先形成(3:1)(2R,3aS)-和(3S,5R)-异恶唑烷衍生物，分别通过在过渡态应用内部烷氧基更具反应活性的构象来预测。这些环加合物分别被对映体转化为(-)-乌头碱和(+)-单乌头碱I。

项目成果

伊藤昌之、樹林千尋: J.Am.Chem.Soc.

伊藤雅之、麒麟千寻：J.Am.Chem.Soc。

Masayuki Ito; Chihiro Kibayashi: "Asymmetric Induction in Nitrone Cycloaddition with a Chiral Allyl Ether. Enantioselective Synthesis of (-)-Coniine and (+)-Monomorine I" J. Am. Chem. Soc.,Submitted.

伊藤雅之；