Organic Synthesis via Transition Metal Complexes (Chemistry)

在自然系统中发现的复杂分子的合成对合成有机化学家提出了越来越高的要求。过渡金属为医学和农业中发现的一系列分子的新方法的开发提供了所需的精细化学控制。有机和大分子化学项目的总体目标是开发使用过渡金属配合物的新合成方法，以允许有机官能团的新反应模式。这将通过仔细研究所涉及的金属有机物种的基本化学来实现，以便开发有用的、新的合成转化。新开发的工艺将在可能的情况下应用于复杂分子的合成。所提出的研究的科学意义在于，将开发用于有机合成的新化学转化，将生产出具有有趣的物理、生物和化学性质的新有机化合物。因此-内酰胺类可由Pd（II）辅助的烯烃氨基羰基化或氨基甲酸乙烯酯合成。各种碳环体系，包括中等大小的熔融双环体系，将由简单的二烯起始原料合成，通过不寻常的“1,3”环加成亲电烯烃和炔烃到pi-烯丙基钯配合物，然后进行还原消除。从（VI）族金属碳烯络合物中新发现的氨基烯酮烯和漆膜烯酮烯将被开发出来，以提供一系列不寻常的有机化合物，包括非天然α -氨基酸和含有非天然氨基酸的肽。这些不寻常的金属结合的烯酮有望在有机合成中有广泛的应用。最后，将开发新的、实用的有机金属碳和亚硝基配合物的合成方法，并评估它们在有机合成中的应用。

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.