NEW SYNTHETIC METHODS USING HIGHLY REACTIVE METALS

使用高活性金属的新合成方法

• 批准号: 3287374
• 负责人: REUBEN D RIEKE
• 金额: $ 12.29万
• 依托单位: UNIVERSITY OF NEBRASKA LINCOLN
• 依托单位国家: 美国
• 财政年份: 1985
• 资助国家: 美国
• 起止时间: 1985-09-01 至 1989-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3287374
• 关键词: alloys; cadmium; chemical kinetics; chemical reaction; chemical structure function; copper; cyclopropanes; drug design /synthesis /production; drug screening /evaluation; iron; lithium; magnesium; nickel; organometallic compounds; oxidation reduction reaction; reagent /indicator; uranium; zinc

The overall objective of this proposal is the development of new synthetic methodologies using highly reactive metal powders. Several new approaches for the preparation of highly reactive metal powders have been developed in our laboratories. These metal powders exhibit far superior reactivity towards oxidative addition reactions than any described for these metals in the literature. Using these metals, a wide variety of new reactions and dramatic extensions of existing reactions are proposed. The metal to be studied include Ni, Cd, Zn, U, Fe, Mg, and Cu. While this study will not be directed towards the synthesis of any one natural product, it is anticipated that the results of this study will be of great value to the synthetic community. Requests from synthetic chemists from all over the USA and the world are constantly coming to our laboratories regarding preparation and use of highly reactive metals developed in our laboratories. The new chemistry proposed in this grant request will provide for several new significant synthetic approaches. The highly reactive magnesium studies should yield valuable extensions of Grignard chemistry. Moreover, the facile generation of a five-membered magnesium metallocycle should prove to be of extensive value. New cyclization reactions using nickel, copper, and magnesium are proposed which will tolerate a wide range of functionality. The ability to generate organocadmium reagents and organocopper reagents directly from alkyl and aryl halides with most any functionality will dramatically increase the utility of these very versatile reagents. A new exciting class of metal-lithium alloys is proposed; one of these may be an entry into highly reactive lithium. Highly reactive zinc is expected to allow the preparation of substituted cyclopropanes in the Simmons-Smith reaction. Also, the direct preparation of dialkyl zinc reagents with a wide variety of functional groups present is most probable. Several new classes of zero valent complexes of Ni and Fe are proposed. The preparation of several new organoiron species are proposed and several cross-coupling reactions with these reagents are suggested. The highly reactive uranium will be used to carry out reductive coupling reactions as well as to generate new organouranium species. The synthetic utility of these new organometallic species will be examined. Finally, this study will provide insight into the origin of high reactivity at a metal surface as well as mechanistic considerations regarding oxidative addition reactions at a metal surface.

该提案的总体目标是开发新的合成 使用高活性金属粉末的方法。 若干新办法 用于制备高活性金属粉末的方法已经在 我们的实验室 这些金属粉末表现出远为优越的上级反应性 对于这些金属的氧化加成反应， 文学作品 利用这些金属，各种各样的新反应， 提出了现有反应的显著扩展。 述金属 所研究的元素包括Ni、Cd、Zn、U、Fe、Mg和Cu。 虽然这项研究不会 针对任何一种天然产物的合成，它是 预计这项研究的结果将具有重要价值， 合成社区 来自世界各地的合成化学家的请求 美国和世界各地不断来到我们的实验室， 我们开发的高活性金属的制备和使用 laboratories. 在这项资助申请中提出的新化学将 提供了几种新的重要合成方法。 高度 活性镁的研究应该产生有价值的推广格利雅 化学. 此外，五元镁的容易生成 应该证明，这是一种具有广泛价值的做法。 新环化 提出了使用镍、铜和镁的反应， 容许广泛的功能。 能够产生 有机镉试剂和有机铜试剂， 具有大多数任何官能度的芳基卤化物将显著增加 这些非常通用的试剂的效用。 一个新的令人兴奋的类 金属锂合金提出;其中之一可能是进入高 活性锂 高反应性锌预期允许 在Simmons-Smith反应中制备取代的环丙烷。 同时，直接制备二烷基锌试剂的方法也有很大的发展空间， 存在的官能团是最有可能的。 几类新的零 提出了Ni和Fe的价络合物。 准备几个新的 提出了有机铁物种和几个交叉偶联反应， 推荐这些试剂。 高活性铀将用于 进行还原偶联反应，并产生新的 有机肥料种类 这些新的有机金属化合物的合成效用 物种将被检查。 最后，这项研究将提供深入了解 金属表面高反应性的起源以及机械性 关于在金属表面的氧化加成反应的考虑。