NEW SYNTHETIC METHODS USING HIGHLY REACTIVE METALS

这项建议的总体目标是开发新的合成材料 使用高活性金属粉末的方法。几种新方法 用于制备高活性金属粉末的技术已经在 我们的实验室。这些金属粉末的反应性要好得多。 对氧化加成反应的反应比对这些金属在 文学作品。使用这些金属，各种各样的新反应和 提出了现有反应的戏剧性扩展。即将成为的金属 研究的元素包括镍、镉、锌、铀、铁、镁和铜。虽然这项研究不会 任何一种天然产物的合成，它是 预期这项研究的结果将对 人工合成社区。来自世界各地的合成化学家的要求 美国和世界不断来到我们的实验室， 我国开发的高活性金属的制备和应用 实验室。在这项拨款申请中提出的新化学将 提供了几种新的重要的合成方法。高度的 活性镁研究应该产生有价值的格氏扩展 化学反应。此外，五元镁的简单生成 金属循环应该被证明具有广泛的价值。新环化 提出了使用镍、铜和镁的反应，这将 支持多种功能。产生的能力 烷基和烷基直接合成的有机镉试剂和有机铜试剂 具有几乎任何官能团的芳基卤化物将显著增加 这些用途非常广泛的试剂。一个新的令人兴奋的班级 金属锂合金被提出；其中之一可能是进入高度 活性锂。高活性锌预计将允许 Simmons-Smith反应中取代环丙烷的制备。 此外，直接制备二烷基锌试剂的种类也很多。 官能团的存在是最有可能的。几个新的零类 提出了镍、铁的价态络合物。几种新产品的制备 提出了有机铁物种和几种交叉偶联反应 建议使用这些试剂。高活性的铀将被用于 进行还原偶联反应以及生成新的 有机铀物种。这些新型有机金属的综合用途 将对物种进行检查。最后，这项研究将提供对 金属表面高反应性的起源及其机理 关于金属表面氧化加成反应的考虑。

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.