SYNTHESIS OF A-HYDROXYCARBONYL COMPOUNDS

A-羟基羰基化合物的合成

• 批准号: 3284379
• 负责人: FRANKLIN A DAVIS
• 金额: $ 9.28万
• 依托单位: DREXEL UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1985
• 资助国家: 美国
• 起止时间: 1985-06-01 至 1988-05-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3284379
• 关键词: acetylation; aziridines; beta lactam antibiotic; carbonyl compound; chelating agents; chemical structure function; drug design /synthesis /production; drug screening /evaluation; enolate; ketones; lactones; metal complex; oxidation; oxygen transport

The aim of the proposed work is to develop methodology for the direct oxidation and asymmetric oxidation of enolates to Alpha-hydroxycarbonyl compounds (R2C(OH)C(O)-Z). Compounds having the Alpha-hydroxycarbonyl structural unit are ubiquitous in nature and responsible, for the biological activity of many compounds having this subunit. These goals will be achieved by exploring the oxidation of enolates (enol silyl ethers, enamines, metaloenamines) using 2-sulfonyloxaziridines, aprotic and neutral oxidizing agents. Oxidation of chiral enolates using these reagents is anticipated to give optically active Alpha-hydroxycarbonyl compounds in high optical purity. Studies of enolate oxidations with chiral 2-sulfonyl- and 2-sulfamyloxaziridines will provide insights into the origins of asymmetric induction and new information on electrophile-enolate trajectories. Metal assisted asymmetric oxidations using 2-sulfamyloxaziridines having metal chelating functional groups are anticipated to give Alpha-hydroxycarbonyl compounds in high enantiotopic purity. This methodology will be applied to the chiral synthesis of (-)-Eucomol and (+)-demethoxydaunomycinone; the latter compound is a potent anti-tumor agent. The feasibility of direct enolate and asymmetric enolate oxidation as a viable synthetic route to Alpha-hydroxycarbonyl compounds has been demonstrated by preliminary studies.

拟议工作的目的是发展直接的方法