Synthetic Applications of the Aza-Achmatowicz Reaction (Chemistry)

Aza-Achmatowicz 反应的合成应用（化学）

• 批准号: 8708130
• 负责人: Marco Ciufolini
• 金额: --
• 依托单位: William Marsh Rice University
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-07-01 至 1990-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8708130&HistoricalAwards=false
• 关键词: Synthetic; Applications; Aza; Achmatowicz; Reaction

This grant in the Organic and Macromolecular Chemistry Program suppports research by Dr. Marco Ciufolini. The methodology being developed by Dr. Ciufolini has the potential for becoming a new standard route for the synthesis of nitrogen containing materials. This class of materials is extremely important in substances found in both medicine and agriculture. The rearrangement of N-acyl-2-furylamines to N-acyl-2-alkyl-piperidin-3-ones (termed the "Aza-Achmatowicz" reaction) will be developed into a general method for the total synthesis of optically active nitrogenous substances. A key step of the new technique involves enzymatic resolution of racemic furylglycines. The resolved aminoacids, which will be stereochemically correlated with (L)-Serine, are readily and efficiently transformed into valuable building blocks for the synthesis of structures as diverse as, e.g., azasaccharides, beta-lactams, unusual aminoacids, and amphibian alkaloids. A number of issues in organic methodology will be confronted in connection with the total synthesis of members of those general classes of compounds. The stereochemical course of enolate alkylations, conjugate additions of organocopper reagents and oxidation reactions will be investigated in detail using the rearranged materials as substrates. The directing effect of N-centered functionalities on the stereochemical course of reactions at neighboring olefinic subunits will be studied. New methodology will be developed based on the chemistry of enamides. Ultimately, the Aza-Achmatowicz reaction will be refined enough to be used for the construction of N-containing carbon frameworks considerably more complex than the ones planned in this research.

有机和高分子化学项目的资助 支持Marco Ciufolini博士的研究。 的方法 由Ciufolini博士开发的技术有可能成为 合成含氮化合物的新标准路线 材料. 这类材料在以下方面极为重要： 在医药和农业中发现的物质。 N-酰基-2-呋喃胺重排为 N-酰基-2-烷基-哌啶-3-酮（称为“Aza-Achmatowicz”） 反应）将发展成为一个通用的方法，为总 光学活性含氮物质的合成。 一个关键 新技术的一步涉及酶促拆分， 外消旋呋喃基甘氨酸。 分解的氨基酸， 与（L）-丝氨酸立体化学相关，容易且 有效地转化为有价值的构建块， 合成多种多样的结构，例如，氮杂糖， β-内酰胺，不常见的氨基酸，和两栖类生物碱。 一 有机方法学中的一些问题将在 与这些一般委员会成员的全面综合有关 化合物的种类。 烯醇化物的立体化学过程 烷基化，有机铜试剂的共轭加成， 氧化反应将详细研究使用 重排的材料作为基底。 的导向作用 立体化学过程中的N-中心官能团 将研究在相邻烯烃亚基处的反应。 新的方法学将根据以下化学物质开发： 酰胺。 最终，Aza-Achmatowicz反应将是 足够精炼以用于构建含N 碳结构比那些 计划在这项研究中。