Exploitation of P-450 Type Catalytic Oxidations and their Application to Organic Synthesis

本研究项目的主要目的是获得非活性有机底物的仿生氧化转化的创新方法，并将其扩展到有机合成和工业过程中。基于用过渡金属催化剂模拟细胞色素P-450单加氧酶酶促功能的新策略，从合成的角度研究了各种过渡金属的生成、反应性和催化作用。由低价钌配合物和过氧化物（如t-BuOOH和AcOOH）产生的氧化钌已被证明是非活性底物氧化的高活性催化物质。因此，在钌催化剂和过氧化物的作用下，可以进行胺、酰胺、酚和烷烃的多种特定氧化反应。这些新反应为非活性底物的转化提供了一种强大的合成方法，包括胺烯烃的仿生环化、胺的α取代和酚合成醌。氧化金属生成原理的扩展导致了在醛存在下的新型有氧氧化。烷烃的好氧氧化可以在温和的条件下在催化量的低价过渡金属催化剂和醛的存在下有效地进行。由于对工业上重要的环己烷氧化的进一步研究，使用cucl_2 -冠醚或氟化钌卟啉钌络合物作为催化剂实现了极高的效率和选择性。

The main aim of the present research project is to acquire innovative method for biomimetic oxidative transformations of unreactive organic substrates and to extend it to the organic syntheses and industrial processes. Based on the new strategy for simulating enzymatic function of cytochrome P-450 monooxygenases with transition metal catalysts, the generation, reactivity and catalysis of various oxometal species of transition metals have been investigated from synthetic viewpopints. Oxoruthenium species generating from low valent ruthenium complexes and peroxides such as t-BuOOH and AcOOH has proven to be highly reactive catalytic species for the oxidations of unreactive substrates. Thus, a variety of specific oxygenation reactions of amines, amides, phenols and alkanes can be performed with ruthenium catalysts with peroxides. These new reactions provides a powerful synthetic method for transformations of unreactive substrates, including biomimetic cyclization of aminoolefins, alpha-substitution of amines, and quinone synthesis from phenols. Extension of the principle of the generation of oxometal species has led to the novel aerobic oxidations in the presence of aldehydes. Aerobic oxidation of alkanes can be performed efficiently under mild conditions in the presence of a catalytic amount of low valent transition metal catalysts and aldehydes. As a consequence of further study focused on the oxidation of industrially important cyclohexane, extremely high efficiency and selectivity have been achieved using CuCl_2-crown ethers or ruthenium fluorinated porphyrin ruthenium complexes as a catalyst.