SYNTHETIC AND MECHANISTIC STUDIES OF ERGOT ALKALOIDS

麦角生物碱的合成及机理研究

• 批准号: 3282300
• 负责人: JULIUS REBEK
• 金额: $ 6.93万
• 依托单位: UNIVERSITY OF PITTSBURGH AT PITTSBURGH
• 依托单位国家: 美国
• 财政年份: 1983
• 资助国家: 美国
• 起止时间: 1983-12-01 至 1986-11-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3282300
• 关键词: chemical reaction; chemical substitution; chemical synthesis; nuclear magnetic resonance spectroscopy; racemization; tryptophan

This proposal explores the use of tryptophan as a starting material for the total synthesis of ergot alkaloids. The methods involve intramolecular Friedel-Crafts reaction of a suitably protected tryptophan to give an optically active tricyclic skeleton ideally functionalized for elaboration to natural products. Either enantiomer is available from L-tryptophan. Specific targets include the ergolines lysergene and lysergol, the chanoclavines and clavicipitic acid. The latter involves a study of intramolecular amido-alkylation of the 4-position of tryptophan from which substances of biosynthetic interest should become available. Finally, a mechanistic study of the peculiar racemization and isomerization behavior of the rugulovasine ergot alkaloids is proposed.

该提案探索了色氨酸作为制备方法的起始材料的用途。 麦角生物碱的全合成。 该方法涉及分子内 适当保护的色氨酸的Friedel-Crafts反应，得到 光学活性三环骨架理想地官能化用于制备 天然产品。 任一对映异构体可得自L-色氨酸。 特异性靶点包括麦角林麦角碱和麦角醇， 裸花黄素和棒菌酸。 后者涉及到一项研究， 色氨酸4位的分子内酰胺基烷基化， 应提供具有生物合成意义的物质。 最后 特殊消旋和异构化行为的机理研究 的rugulovasine麦角生物碱的建议。