ASYMMETRIC THERMAL ADDITION AND CYCLOADDITION REACTIONS

不对称热加成和环加成反应

• 批准号: 3279899
• 负责人: DENNIS P CURRAN
• 金额: $ 14.32万
• 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/3279899
• 关键词: Diels Alder reaction; alkenes; alkyl nitrile; carbonyl compound; 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.

该提案是一个与原始提案不同的竞争性延续 重大新研究主题（羟醛加合物的环加成路线） 方向。 相对和绝对立体化学的控制是 现代有机合成的中心焦点。 已经取得了巨大的进步 传统上重要转化的立体化学控制 如羟醛反应、第尔斯-阿尔德环加成反应和烯醇化物 烷基化。相对和绝对立体化学的控制 通过热进行的重要加成和环化反应 （而不是金属促进的）途径知之甚少，并且这些 因此，反应的利用频率较低。 这次的两个目标 提案将受到同等重视：1）开发新的、 立体控制的热加成和环化反应，以及2) 了解控制立体化学的潜在因素。 研究目标有两大类反应：1) 偶极反应 环加成-已经有一个可以构建的基础， 2）自由基反应，其中缺乏立体控制反应 自由基在合成中的重要性日益增加，需要立即 学习。 在这个早期阶段，该项目的目标非常明确 基础（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创而有力的解决方案 生物医学活性化合物的合成即将进行。