NEW SYNTHETIC METHODS USING HIGHLY REACTIVE METALS

这项建议的目标是开发新型高活性 金属粉末及其他高活性零价和阴离子金属 这些品种可以用来开发各种新的合成方法。 聚合物基质中高活性金属的制备也将是 检查过了。制备高活性有机硅的几种新方法 我们实验室已经开发出金属粉末。1-3这些金属 粉末对氧化加成的反应性要好得多 比文献中对这些金属的任何描述的反应都要多。这个 高活性金属粉末与多种有机化合物的反应 基板有望带来一系列新的和新颖的产品 有机金属化合物。预计会有几种新的合成方法 是这些研究的结果。要研究的主要金属包括 铜、镁、锌、钙。与其他金属相比，高活性的 铜似乎是一种均质的络合物。零价络合物高度 可溶于有机溶剂，其反应活性高度依赖于 用于还原铜盐的初始配体(即膦， 硫化物等)。我们提出了一种Cun.Ly铜团簇结构 这些化合物。零价铜预计将与广泛的 光谱有机底物生产多种新型有机铜 试剂，这将导致一些新的合成方法。 提出了几种新的分子内过程。中的主要功能 这些反应中的大多数将是生成有机铜的能力 氧化法直接从高官能化有机卤化物中提取物种 将零价铜加到碳-卤键上。高度的 已发现活性铜很容易转化为含有卤素的 聚合物变成铜衍生物，可以与各种不同的 亲电者。含有高活性的聚合物，附着在 已经制备了聚合物主链，并对这种新的合成用途进行了研究 将对试剂进行检查。本文还提出了一种新型的铜阴离子。这个 已发现高活性镁很容易与1，3-二氯苯酚反应。 丁二烯生成镁金属环。初步结果显示 表明该双格氏试剂可与多种 亲电者。高活性锌有望导致合成 高官能化有机锌试剂的研究进展 分子内西蒙斯-史密斯化学。一种高活性物质的研究 还提出了可溶性钙络合物的概念。

The objective of this proposal is the development of novel highly reactive metal powders and other highly reactive zero-valent and anionic metal species which can be used to develop a variety of new synthetic methods. Preparation of the highly reactive metals in a polymer matrix will also be examined. Several new approaches for the preparation of highly reactive metal powders have been developed in our laboratories.1-3 These metal powders exhibit far superior reactivity towards oxidative addition reactions than any described for these metals in the literature. The reactions of the highly reactive metal powders with a variety of organic substrates is expected to lead to a wide spectrum of new and novel organometallic compounds. Several new synthetic methodologies are expected to result from these studies. The principal metals to be studied include Cu, Mg, Zn, and Ca. In contrast to the other metals, the highly reactive Cu appears to be a homogeneous complex. The zero-valent complex is highly soluble in organic solvents and its reactivity is highly dependent on the initial ligand used in the reduction of the copper salt (i.e. phosphine, sulfide, etc.). We are proposing a Cu n.Ly copper cluster structure for these compounds. The zero-valent copper is expected to react with a wide spectrum of organic substrates to produce a number of new organocopper reagents which should lead to a number of novel synthetic approaches. Several novel intramolecular processes are proposed. The key feature in most of these reactions will be the ability to generate organocopper species directly from highly functionalized organohalides by oxidative addition of the zero-valent copper to carbon-halogen bonds. The highly reactive copper has been found to readily convert halogen containing polymers into copper derivatives which can be cross-coupled with various electrophiles. Polymers containing the highly reactive attached to the polymer backbone have been prepared and the synthetic utility of this new reagent will be examined. A novel copper anion is also proposed. The highly reactive magnesium has been found to readily react with 1,3- butadienes to generate a magnesium metallocycle. Preliminary results have indicated that this bis-Grignard reagent will react with a variety of electrophiles. Highly reactive zinc is expected to result in the synthesis of highly functionalized organozinc reagents as well as the development of intramolecular Simmons-Smith chemistry. The study of a highly reactive soluble calcium complex is also proposed.