A New Approach to Selective Noble Metal Catalysts

选择性贵金属催化剂的新方法

• 批准号: 7208967
• 负责人: MICHEL R GAGNE
• 金额: $ 25.02万
• 依托单位: UNIV OF NORTH CAROLINA CHAPEL HILL
• 依托单位国家: 美国
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-05-15 至 2010-02-28
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7208967
• 关键词: Affective; Alkenes; Benchmarking; Carbon; Catalysis; Cations; Chemicals; Chemistry; Class; Closure; Complex; Condition; Couples; Cyclization; DNA Sequence Rearrangement; Development; Development Plans; Exercise; Generations; Goals; Metals; Object Attachment; Palladium; Pathway interactions; Polyenes; Procedures; Process; Range; Reaction; Research; Route; Salts; Scheme; Skeletal system; Transition Elements; analog; catalyst; coping; design; diene; novel strategies

DESCRIPTION (provided by applicant): The design and execution of reliable complexity enhancing chemical transformations continues to be a goal at the forefront of synthesis. Since transition metal catalysts increase efficiency and enable new routes to complex molecules, their utility will continue to grow. This proposal outlines a research plan for developing a broad class of metal catalyzed reactions that utilize the electrophilic ring closure of 1,5- and 1,6-dienes, to generate cationic intermediates capable of participating in and initiating a wide range of reactions. The products of metal catalysis are unique in that they are under CATALYST CONTROL, which enables the transformations to be made with control of enantioselectivity, regioselectivity, and skeletal connectivity. In contrast to purely ionic means to cationic chemistry, a significantly greater degree of reaction control can be exercised. SPECIFIC AIMS (1) To develop a palladium-catalyzed reaction that cyclo-generates reactive "cations" from 1,5- and 1,6-dienes for subsequent trapping, rearrangement, and ring-annulat!ve cation-olefin reactions. (2) To develop pincer- and pseudo-pincer electrophilic catalysts for polyene activation/cation generation and cycloisomerization catalysis. (3) To develop intermolecular C-C bond forming reactions that generate trappable intermediate cations for cascade reactions (e.g. Prins reaction).

描述（由申请人提供）：设计和执行可靠的复杂性增强化学转化仍然是合成的最前沿目标。由于过渡金属催化剂提高了效率，并使复杂分子的新途径成为可能，因此它们的实用性将继续增长。该提案概述了一个研究计划，开发一个广泛的金属催化反应，利用亲电环闭合的1，5-和1，6-二烯，产生阳离子中间体能够参与和引发广泛的反应。金属催化的产物是独特的，因为它们处于催化剂控制之下，这使得能够在控制对映选择性、区域选择性和骨架连接性的情况下进行转化。与纯离子方式到阳离子化学相反，可以实施显著更大程度的反应控制。具体目标（1）开发一种钯催化的反应，从1，5-和1，6-二烯环生成活性“阳离子”，用于随后的捕获，重排和环annulat！ve阳离子-烯烃反应。(2)开发钳形和拟钳形亲电催化剂用于多烯活化/阳离子生成和环异构化催化。(3)开发分子间C-C键形成反应，为级联反应（例如Prins反应）生成可捕获的中间阳离子。