ASYMMETRIC PHOTOADDITION OF CHIRAL ALLENES

手性八烯的不对称光加成

• 批准号: 2190182
• 负责人: ERICK M. CARREIRA
• 金额: $ 16.78万
• 依托单位: CALIFORNIA INSTITUTE OF TECHNOLOGY
• 依托单位国家: 美国
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-04-01 至 2000-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2190182
• 关键词: carbopolycyclic compound; chemical addition; chemical group; chemical substitution; chemical synthesis; diene; ketones; photochemistry; stereochemistry; stereoisomer; tannins

DESCRIPTION: In this revised application, the principal investigator states that the intramolecular photocycloaddition reaction of allenes with enoates and enones is a powerful tool for the construction of carbon-carbon bonds in stereochemically complex, polycyclic structures. He reports the he has observed asymmetric induction in the photocyclization and photoaddition reactions of chiral 1,3-disubstituted allenes with an enone in which asymmetry is derived exclusively from the allene fragment. He notes that on the basis of these results, the aims of this proposal are (1) examination of carbocyclic allene-enones and allene-coumarins as substrates for the intramolecular, asymmetric photocycloaddition (2) to develop a detailed understanding of the mechanism of these transformations and develop a paradigm for the prediction of stereochemistry (3) to develop a family of optically active 1,3- disubstituted allenes with removable auxiliary substituents, and (4) the application of the enantioselective allene-enone photoaddition reaction to the synthesis of the biologically active tannin chebulic acid. It is reported that chebulic acid and related tannins exhibit potent antitumerogenic activity by inhibition of calf thymus and human colon adenocarcinoma topoisomerase I.

描述：在此修订的应用程序中，首席调查员 指出艾伦的分子内光载体反应 使用Enoates和Enones是建造的强大工具 立体化学复杂的多环结构中的碳碳键。 他报告说他已经观察到了不对称的诱导 手性1,3-取代的光循环和光圈反应 艾伦带有一个，其中不对称仅从 Allene碎片。 他指出，根据这些结果，目的 该提议的是（1）检查碳纤维丙烯酸烯烯烃和 艾琳 - 美甘林作为分子内，不对称的底物 Photocycloadition（2）以详细了解 这些转换的机制，并为 立体化学的预测（3）以开发一个光学上的家族 活性1,3-脱取的，带有可移动辅助取代基， （4）对映选择性艾烯烯烃的应用 对生物活性单宁合成的光辅助反应 切布酸。 据报道，切布酸和相关的单宁 通过抑制胸腺和 人类结肠腺癌拓扑异构酶。