ASYMMETRIC THERMAL ADDITION AND CYCLOADDITION REACTIONS

不对称热加成和环加成反应

• 批准号: 2176248
• 负责人: DENNIS P CURRAN
• 金额: $ 16.65万
• 依托单位: UNIVERSITY OF PITTSBURGH AT PITTSBURGH
• 依托单位国家: 美国
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-12-01 至 1994-11-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2176248
• 关键词: Diels Alder reaction; alkenes; alkyl nitrile; carbonyl compound; chemical addition; chemical bond; chemical reaction; chemical synthesis; cyclization; cycloalkene; cyclopentane; hydrogen bond; phenylamide; stereochemistry; temperature

This proposal is a competing continuation that departs from the original research theme (cycloadditive route to aldol adducts) in significant new directions. The control of relative and absolute stereochemistry is a central focus in modern organic synthesis. Great strides have been made in stereochemical control of traditionally important transformations like aldol reactions, Diels-Alder cycloadditions, and enolate alkylations. The control of relative and absolute stereochemistry in important addition and cyclization reactions that proceed by thermal (rather than metal-promoted) pathways is less understood, and these reactions are therefore exploited less frequently. Two goals of this proposal will receive equal emphasis: 1) the development of new, stereocontrolled thermal addition and cyclization reactions, and 2) the understanding of the underlying factors that control stereochemistry. Two broad classes of reactions are targeted for study: 1) dipolar cycloadditions-where there is already a foundation on which to build, and 2) radical reactionswhere the paucity of stereocontrolled reactions and the growing importance of radicals in synthesis demand immediate study. At this early stage, the goals of the project are very fundamental (development and understanding of new reactions). However, exciting preliminary results indicate that these goals are realistic, and that original and powerful solutions to important problems in the synthesis of biomedically active compounds will be forthcoming.

该提议是一个竞争的延续，偏离了原始 研究主题（通往Aldol加合物的CycloadDitive途径） 方向。 相对和绝对立体化学的控制是 现代有机综合中的中心重点。 大步很大 在传统重要转变的立体化学控制中 像aldol的反应，Diels-Alder Cycloaditions和酸化 烷基化。对相对和绝对立体化学的控制 重要的添加和环化反应，以热进行 （而不是金属促进的）途径较少了解，而这些途径 因此，反应的频率较低。 两个目标 提案将得到同等的重点：1）新的发展， 立体控制的热添加和环化反应，以及2） 了解控制立体化学的基本因素。 两种广泛的反应是针对研究的：1）偶极 Cycloaditions-已经有一个基础可以建立的基础 2）立体控制反应的根本反应很少 以及激进分子在合成需求中的重要性日益立即 学习。 在这个早期阶段，该项目的目标非常 基本（对新反应的发展和理解）。 然而， 令人兴奋的初步结果表明这些目标是现实的， 以及针对重要问题的原始和强大的解决方案 生物医学活性化合物的合成将即将到来。