NEW SYNTHETIC METHODS USING HIGHLY REACTIVE METALS

该提案的目标是开发新型高活性的 金属粉末和其他高活性零价和阴离子金属 可用于开发各种新的合成方法。 在聚合物基质中制备高反应性金属也将是有利的。 考察 制备高活性聚乙烯的几种新方法 我们的实验室已经开发了金属粉末。1 -3这些金属 粉末对氧化加成表现出远为优越的上级反应性 反应比文献中对这些金属所描述的任何反应都要快。 的 高活性金属粉末与各种有机化合物的反应 基板有望导致广泛的新的和新颖的 有机金属化合物 预计将有几种新的合成方法 这些研究的结果。 要研究的主要金属包括 Cu、Mg、Zn和Ca。 与其他金属相比， 铜似乎是一个均匀的配合物。 零价络合物是高度 可溶于有机溶剂，其反应性高度依赖于 用于铜盐还原的初始配体（即膦， 硫化物等）。 我们提出了一种Cu n.Ly铜簇结构， 这些化合物。 零价铜预计将与广泛的 光谱的有机底物，以产生一些新的有机铜 这将导致许多新的合成方法的试剂。 提出了几种新的分子内过程。 中的关键特征 这些反应中的大多数将能够生成有机铜， 直接从高度官能化的有机卤化物通过氧化 将零价铜加成到碳-卤素键上。高度 已经发现活性铜容易将含卤素的 聚合物转化为铜衍生物，其可以与各种 亲电体 聚合物含有高反应性连接到 聚合物主链已经制备，并且这种新的聚合物主链的合成效用已经被证实。 将对试剂进行检查。 还提出了一种新的铜阴离子。 的 已经发现高活性镁容易与1，3- 丁二烯以产生镁丁二烯。 了初步成效 表明这种双格氏试剂将与多种 亲电体 高活性锌预期导致合成 高度官能化的有机锌试剂以及 分子内西蒙斯-史密斯化学 研究了一种高活性 还提出了可溶性钙络合物。

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.