NEW SYNTHESIS OF BIOCHEMICAL WITH HOMOGENEOUS CATALYSTS

我们的最终目标是设计和开发多功能多功能 使我们能够进行多步合成的催化剂系统 以一种高度有组织的方式在一锅中。作为一个基本的 为了实现这一具有挑战性的目标，我们将发起和推动 “均相生物化学新合成”的研究 本项目包括四个分项目。(一)说明 立体化学法酰胺化反应机理的研究 方法，其中我们将解决一个历史之谜，即水 在高价金属离子存在下选择性地裂解酰基钴键 压力氢气，通过设计双环中间体轴承 严格的立体要求，这样我们就可以毫不含糊地 区分提出的可能机制。(Ii)螯合- 定向的区域和立体控制，在那里我们 将首次系统地引入螯合控制， 并将其应用于催化不对称 综合。(3)分子内氨甲酰化反应的应用 氮杂环的合成，我们将在其中发展 生物活性化合物的高效合成新方法 氮杂环，尤其是生物碱的中间体。 (IV)CoRh(CO)7反应机理的高压FT-IR研究 这种独特的混合金属团簇的行为 将对氢甲酰化进行研究- 酰胺化工艺。

Our ultimate goal is to design and develop multi-functional multi- catalyst systems which enable us to carry out multi-step synthesis in one-pot in a highly organized manner. As a fundamental approach to this challenging goal, we will initiate and promote the research on the "new synthesis of biochemicals with homogeneous catalysts". This project includes four subprojects. (i) Elucidation of the mechanism of amidocarbonylation by stereochemical approach, in which we will solve a historical mystery, i.e., water cleaves acylcobalt bond selectively in the presence of high pressure hydrogen, by designing bicyclic intermediates bearing strict steric requirements so that we can unambiguously distinguish the possible mechanisms proposed. (ii) Chelation- directed regio- and stereocontrol in carbonylations, in which we will systematically introduce chelation control, for the first time, to carbonylations and apply it to the catalytic asymmetric synthesis. (iii) Applications of intramolecular amidocarbonylation' to the synthesis of nitrogen heterocycles, in which we will develop efficient new methods for the synthesis of biologically active nitrogen heterocyles, especially the intermediates for alkaloids. (iv) High pressure FT-IR study on the mechanism of CoRh(CO)7 catalysis in which the behavior of this unique mixed-metal cluster will be studied regarding the hydroformylation- amidocarbonylation process.