【作者】 龚天军；

【导师】 刘有成； 傅尧；

【作者基本信息】 中国科学技术大学 ， 有机化学， 2014， 博士

【摘要】 过渡金属催化C-H活化提供了绿色、原子经济的化学合成方法。多种过渡金属(Pd、Ru、Ir等)催化的C-H活化官能化反应得到广泛的研究。近年来,Rh(III)催化C-H活化反应也得到了充分的发展,并为重要活性药物分子合成提供了有效的方法。该论文首先综述了Rh(III)催化C-H活化烯基化、烷基化、氨化等官能化反应以及在杂环合成上的应用。从而得出结论,进一步发展Rh(Ⅲ)催化C-H活化官能化反应及杂环化合物合成的新方法,并实现重要活性药物分子的合成,仍是有机合成化学中一项重要的课题。1. Rh催化酚酯导向C-H活化氧化Heck反应。我们首次实现酚酯导向的氧化Heck反应。反应可以有效的兼容Br, Cl等基团；多种烯烃底物都可以得到很好的反应。与Pd(Ⅱ)催化的Heck反应相比,反应实现很好的区域选择性控制。反应提供了合成2-烯基取代苯酚衍生物有效方法。2. Rh催化C-H活化与联烯反应合成共轭烯烃反应。我们实现了Rh催化下C-H活化与联烯化合物反应合成共轭烯烃化合物。反应不仅可以实现烯烃C-H底物的反应,芳基C-H底物也可以得到很好的实现。反应产物可以转化为为其他重要骨架分子。3.Rh催化C-H活化氰基化反应。首次实现了RRh(Ⅲ)催化下的C-H活化氰基化反应合成芳基腈化合物。反应使用NCTS作为氰基试剂来源,这是一种低毒易得的氰基化试剂。多种导向基都可以实现邻位的C-H活化氰基化反应；反应可以很好的兼容Br、I、酚羟基、环氧等重要的基团；芳香杂环底物也能得到很好的反应效果；反应可以实现复杂分子的C-H氰基化衍生。4. Rh催化C-H活化合成2-甲基吲哚化合物。我们成功实现了Rh(Ⅲ)催化下,乙酰苯胺衍生物与烯丙醇酯反应得到2-甲基吲哚化合物。反应具有很好的官能团兼容性,Br、I、杂环等重要基团都可以很好的兼容；反应产物可以经过转化得到其他重要结构的化合物；并且我们实现了从简单酰胺原料出发合成两个重要的药物分子。更多还原

【Abstract】 Transition-metal catalyzed C-H bond activation provides an atom-and step-economical approach for organic synthesis. A variety of transition metals (Pd, Ru, Ir, etc.) catalyzed C-H activation functionalization reaction have been developed. In the past five years, Rh (Ⅲ) catalyzed C-H activation reactions have been fully developed, and provides an effective method for the synthesis of biologically active compounds. This paper first reviews the Rh(III) catalyzed C-H activation functionalization reactions and application in the synthesis of heterocyclic. Notwithstanding these pioneering examples, further development of Rh(III) catalyzed C-H activation reactions reactions is needed in synthetic organic chemistry.1. Rhodium-Catalyzed C-H Activation/Olefination of Phenol Carbamates. We reported a practical protocol for ortho C-H activation/olefination of phenol carbamates. The reaction tolerates a variety of important functional groups (aryl-Br, aryl-Cl) and many different olefins can be used in this process. This reaction exhibits different reactivity as compared to the Pd-catalyzed processes, this method provide a new approach for the synthesis of ortho-substituted phenols.2. Rh-catalyzed C-H bond activation with allenes to produce highly unsaturated conjugated olefins. Rh(Ⅲ) catalyzed C-H bond activation with allenes to produce unsaturated conjuncted olefins was reported. The reaction is applicable to both olefin and arene C(Sp2)-H, compatible with varieties of functional groups. The obtained products can be transformed into other important skeletons.3. Rhodium-catalyzed Directed C-H Cyanation. We report the first example of Rh-catalyzed directed C-H cyanation. N-Cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS), a user-friendly cyanation reagent, was used in the transformation. Many different directing groups can be used in this cyanation process and the reaction tolerates a variety of important functional groups (aryl-Br, aryl-I unprotected phenol, epoxide), A number of heteroaromatic nitriles were successfully synthesized by using this method, the reaction may provide a practical tool for rapid derivatization of bioactive compounds.4. A practical Rh-catalyzed reaction was developed to achieve2-alkyl-substituted indoles synthesis. The reaction can tolerate a variety of synthetically important functional groups (aryl-Br, aryl-I, heterocycle). The indole products can also be transformed into other important skeletons. Two bioactive compounds, i.e. indomethacin and pravadoline were prepared using the new method.更多还原