NEW SYNTHETIC METHODS USING HIGHLY REACTIVE METALS

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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.