Some Fundamentally New Organocopper Chemistry

抗生素等复杂天然产物的合成需要高度选择性的反应。这项工作将提供来自相对简单的起始材料的新的有机金属试剂，这项工作得到了有机化学和高分子化学计划的支持。有机铜化学的几个新方面将被研究，包括(1)使用手性高阶铜酸盐进行手性诱导；(2)研究gegenion对铜酸盐的影响，包括第一批非锂和非含镁试剂的生成；(3)Lewis酸在铜酸盐化学中的作用；(4)金属和铜之间的配体交换的第一个例子，以及随后的铜酸盐化学；以及(5)这些新试剂在合成多烯大环内酯类抗生素罗法拉米币中的应用。

The synthesis of complex natural products such as the antibiotics requires highly selective reactions. This work, which will provide new organometallic reagents derived from relatively simple starting materials, is supported in the Organic and Macromolecular Chemistry Program. Several new aspects of organocopper chemistry are to be studied including (1) a search for chiral induction using chiral higher order cuprates; (2) a study on the effect of gegenions on cuprates, including the generation of the first non-lithio and non-magnesio-containing agents; (3) a study on the role of Lewis acids in cuprate chemistry; (4) the first example of the exchange of ligands between a metal and copper, with subsequent cuprate chemistry; and (5)the utilization of these new reagents in the synthesis of the polyene macrolide antibiotic roflamycoin.