Asymmetric Synthesis of Heterocyclic Compounds

杂环化合物的不对称合成

• 批准号: 60571009
• 负责人: NAITO Takeaki
• 金额: $ 0.9万
• 依托单位: Kobe Women's 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: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-60571009/
• 关键词: Asymmetric Synthesis; Heterocyclic Compounds; Enamides; Isoquinoline; Indole; Photocyclization; Alkaloids; エメチン

A new and simple synthetic methodology for the optically active heterocyclic compounds was developed by the application of two types of chiral circumstances to the photocyclizations of the anilides and enamides which are known to proceed via a common intermediate having two functional groups, the enolate and iminium moieties.1. Asymmetric synthesis of quinolones by photocyclization of anilides involving enantioselective protonation of enolate moiety When we used a chiral dibasic acid possessing a <C_2> axis such as di-p-toluoyltartaric acid during the course of irradiation of anilides, optically active quinolones were obtained as a result of enantioselective protonation to the intermediate in moderate chemical and optical yields.2. Asymmetric synthesis of isoquinolines and related compounds by photocyclization of enamides involving enantioselective reduction of iminium moiety Irradiation of enamides in the presence of chiral metal hydride complex of lithium aluminum hydride-chiral amino-alcohol afforded the optically active 8-oxoberbines, thus completing the asymmetric synthesis of (-)-Xylopinine.

本文提出了一种新的、简单的光学活性杂环化合物的合成方法，即利用两种手性环境，通过一个具有两个官能团的中间体（烯醇化物和亚胺），使苯胺和烯酰胺发生光环化反应.苯胺类化合物的光环化反应及烯醇化部分的不对称质子化反应喹诺酮类化合物的不对称合成当我们在苯胺类化合物的光环化反应中使用具有轴的手性二元酸<C_2>如二对甲苯甲酰酒石酸时，由于中间体的不对称质子化反应，以中等的化学产率和光学产率得到了光学活性的喹诺酮类化合物.烯酰胺光环化亚胺还原不对称合成异喹啉及其相关化合物在手性铝锂-手性氨基醇金属氢化物存在下，烯酰胺经光辐射得到光学活性的8-氧代小檗碱，从而完成了（-）-木品宁的不对称合成。

项目成果

Takeaki Naito: "Reductive Photocyclization of Enamide in the Presence of a Chiral Metal Hydride Complex-Asymmetric Synthesis of Xylopinine" Heterocycles. 16. 1141-1143 (1981)

Takeaki Naito：“手性金属氢化物络合物存在下烯酰胺的还原光环化-Xylopinine的不对称合成”杂环。

Takeaki Naito: The Research Foundation for Pharmaceutical Sciences. Reductive Photocyclization of Enamides and Asymmetric Synthesis of Alkaloids, 88-104 (1985)

内藤武明：药物科学研究基金会。

内藤猛章: J.Chem.Soc.,Chem.Commun.,. 1611-1612 (1985)

内藤武明：J.Chem.Soc.，Chem.Commun.，1611-1612 (1985)

内藤猛章: J.Chem.Soc.,Perkin Trans.l,. 487-491 (1985)

内藤武明：J.Chem.Soc.，Perkin Trans.l，487-491 (1985)

Takeaki Naito: "A General Strategy for the Synthesis of Ipecac and Heteroyohimbine Alkaloids" J. Chem. Soc., Chem. Commun.,. 1611-1612 (1985)

Takeaki Naito：“吐根和杂育亨宾生物碱合成的一般策略”J. Chem。