Organic Synthesis via Transition Metal Complexes (Chemistry)

自然系统中复杂分子的合成 对合成有机化学家的要求越来越高。的 过渡金属提供了精细的化学控制所需的 开发了一系列分子的新方法 医学和农业。 这项赠款在有机和 高分子化学计划是开发新的合成 使用过渡金属络合物的方法， 有机官能团的反应性。 完成这项工作的方法是 通过仔细研究金属的基本化学性质 所涉及的有机物种，以允许开发有用的， 新的合成变换。 新开发的工艺 将应用于复杂分子的合成， 可能 拟议研究的科学意义 是新的化学转换一般用于有机 合成将被开发，新的有机化合物， 有趣的物理，生物和化学特性将是 制作。 因此，β-内酰胺将由Pd（II）合成。 烯烃或氨基甲酸乙烯酯的辅助氨基羰基化。 一 各种碳环系统-包括中型稠合 双环体系将由简单的二烯起始 通过亲电的不寻常的“1，3”环加成反应， 烯烃和炔转化为π-烯丙基钯络合物， 还原消除 一种新发现的光生氨基烯酮和 来自第（VI）族金属碳烯络合物的烯氨基烯酮将是 是为了提供一系列不寻常的有机化合物， 包括非天然的α-氨基酸和肽， 非天然氨基酸 这些不寻常的金属结合烯酮是 预期在有机合成中具有广泛的用途。 最后，新的，实用的，有机金属的合成方法 将开发卡宾和氮烯络合物， 有机合成将被评估。

The synthesis of complex molecules found in natural systems places increasing demands on the synthetic organic chemist. The transition metals offer the fine chemical control needed for the development of new methods for a range of molecules found in medicine and agriculture. The overall objective of this grant in the Organic and Macromolecular Chemistry Program is to develop new synthetic methods using transition metal complexes to permit new modes of reactivity for organic functional groups. This will be achieved by careful study of the fundamental chemistry of the metal- organic species involved, to permit the development of useful, new synthetic transformations. The newly developed processes will be applied to the synthesis of complex molecules when possible. The scientific significance of the proposed research is that new chemical transformations of general use for organic synthesis will be developed, that new organic compounds with interesting physical, biological, and chemical properties will be produced. Thus beta-lactams will be synthesized by Pd(II) assisted aminocarbonylatin of olefins or vinyl carbamates. A variety of carbocyclic systems - including medium sized fused bicyclic systems will be synthesized from simple diene starting materials by an unusual "1,3" cycloaddition of electrophilic olefins and alkynes to pi-allylpalladium complexes followed by reductive elimination. A newly discovered photogeneration of aminoketenes and enaminoketenes from Group (VI) metal carbene complexes will be developed to provide an array of unusual organic compounds, including unnatural alpha-amino acids and peptides containing unnatural amino acids. These unusual metal-bound ketenes are expected to have broad utility in organic synthesis. Finally, new, practical, synthetic approaches to organometallic carbene and nitrene complexes will be developed and their utility in organic synthesis will be assessed.