Preparation of Amido-amidate Metallacycles for Polypeptide Synthesis

在有机和大分子化学项目的支持下，加州大学圣巴巴拉分校化学和材料科学系的Timothy J. Deming教授正在研究酰胺-酰胺金属环的合成及其在多肽催化制备中的应用。通过分析低价金属配合物与氨基酸n -羧酸氢化物（NCA）衍生物的反应性，说明NCA与过渡金属反应性的通用性，并开发新的NCA聚合引发剂候选物。在NCA聚合中，酰胺-酰胺金属环是一种活跃的繁殖物质，它的替代合成路线将提供更有效的引发剂，并允许多肽末端功能化的多功能性。通过与具有新的，明确的配位几何结构的酰胺-酰胺金属环合作，将探索立体控制的NCA聚合。多肽是生物利用的主要大分子之一。这些大分子，由许多氨基酸连接在一起，显示出广泛的重要的物理和化学性质。多肽制备的新方法为高效合成分子提供了希望，这些分子有望显示出新的和/或不寻常的性质，包括离子的选择性运输。Timothy J. Deming教授是加州大学圣巴巴拉分校化学与材料科学系的教授，他的多肽合成新催化技术的研究得到了有机和大分子化学项目的支持，为具有独特分子结构的复杂多肽的选择性和高效合成提供了希望。

With the support of the Organic and Macromolecular Chemistry Program, Professor Timothy J. Deming, of the Departments of Chemistry and Materials Science at the University of California, Santa Barbara, is studying the synthesis of amido-amidate metallacycles and their use for the catalytic preparation of polypeptides. Through analysis of the reactivity of low-valent metal complexes with amino acid N-carboxyanhydride (NCA) derivatives, the generality of NCA reactivity with transition metals will be illustrated and new candidates for NCA polymerization initiators will be developed. Alternate synthetic routes to amido-amidate metallacycles, the active propagating species in NCA polymerization, will provide more efficient initiators and allow versatility in the end-functionalization of polypeptides. By working with amido-amidate metallacycles with new, well-defined coordination geometries, stereocontrolled NCA polymerization will be explored.Polypeptides represent one of the major classes of macromolecules utilized by living organisms. These large molecules, comprised of many amino acids linked together, display a wide range of important physical and chemical properties. New approaches to the preparation of polypeptides offer promise for the efficient synthesis of molecules anticipated to display new and/or unusual properties, including the selective transport of ions. Professor Timothy J. Deming, of the Departments of Chemistry and Materials Science at the University of California, Santa Barbara, is supported by the Organic and Macromolecular Chemistry Program for his studies of new catalytic techniques for polypeptide synthesis, offering promise for the selective and efficient synthesis of complex polypeptides with unique molecular architectures.