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Rh(Ⅱ)催化氧化串联反应合成吡咯并[2,1-a]异喹啉衍生物的研究
王宏图
Thesis Advisor卢崇道
2012-05-27
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Name硕士
Degree Discipline有机化学
Keyword铑(ⅱ)催化 氧化 串联反应 吡咯并[2 1-a]异喹啉 Μ2-oh氧桥铁配合物
Abstract

吡咯并[2,1-a]异喹啉衍生物作为一种非常重要的生物碱,表现出诸多优良的生物活性,有关吡咯并[2,1-a]异喹啉结构的合成研究激起了有机化学家浓厚的兴趣。 对于吡咯并[2,1-a]异喹啉衍生物的合成,过去多是由1,3-偶极环化成反应、Michael加成、Heck偶联、Suzuki偶联、环转化等多个反应组合逐步完成的,有时还需要制备特定结构的化合物作为反应的前驱体,反应中会形成较多的副产物,反应效率不高。串联反应以其高效性、操作简便的优点被证明是一种非常实用的制备合成手段,基于此,我们尝试开发一种条件温和、快速高效的串联反应以实现吡咯并[2,1-a]异喹啉衍生物的高效合成。 对于该类串联反应的探索,我们成功开发了一种在铑(Ⅱ)催化剂作用下串联氧化-[3+2]环加成-芳构化反应合成吡咯并[2,1-a]异喹啉衍生物的新方法。2-(3,4-二氢异喹啉-2(1H)-基)乙酸乙酯在Rh2(cap)4催化下,以过氧化叔丁醇(TBHP)为氧化剂,生成亚胺,在碱作用下脱去质子后,随之被亲偶极体原地捕捉得到[3+2]环加成产物;此时反应体系中加入NBS,可以氧化得到吡咯并[2,1-a]异喹啉衍生物。并且,以2-(3,4-二氢异喹啉-2(1H)-基)乙酸乙酯与N-苯基马来酰亚胺的反应为例,考察了催化剂浓度、溶剂、碱等多种因素对于反应的影响。同时,我们对反应体系的适用范围进行了扩展,反应底物具有良好的适用性。 另外,初步尝试了铁盐与N,N′,N″,N'''-四(2-吡啶甲基)-1,4,8,11-四氮杂环十四烷烃(tpmc)配位生成配合物的合成工作,其间合成得到了特征性的μ2-OH氧桥双核络合物[Fe2(μ2-OH)(tpmc)](ClO4)3•CH3CH2OH。但遗憾的是,实验表明该类配合物在催化氧化碳氢键方面,不具备明显的催化活性。

Other Abstract

Pyrrolo [2,1-a] isoquinolines have been recognized as an important class of alkaloids with lots of promising and excellent biological activities. These alkaloids have provoked organic chemists a great deal of interest in their synthetic approaches. According to the previous works, the traditional methods used to synthesize pyrrolo [2,1-a] isoquinolines derivatives are stepwise chemical processes that contain some isolated reactions, such as 1,3-dipolar cycloaddition reactions, Michael addition, Heck coupling reaction, Suzuki coupling reaction, 1,5-electrocyclisation, and so on. Sometimes these protocols need specific and complicated compounds as substrates and lead to substantial byproducts. Thus, exploration of efficient methods toward the syntheses of pyrrolo [2,1-a] isoquinolines derivatives is highly desired. Tandem reactions have proven to be extremely useful and practical synthetic strategy owing to their high reaction efficiency and operational simplicity. Our interest in tandem transformations led us to explore its capabilites in the construction of pyrrolo [2,1-a] isoquinoline skeleton. An efficient method to synthesize pyrrolo [2,1-a] isoquinolines was developed by employing a rhodium(Ⅱ)-catalyzed oxidation/[3+2] cycloaddition/oxidative aromatization cascade. In the presence of Rh2(cap)4 catalyst ethyl 2-(3,4-dihydroisoquinolin-2(1H)-yl)-acetate could be oxidized by tert-butylhydroperoxide to generate the imino compound, whith is deprotonated with base and trapped in situ by dipolarphilic to form [3+2] cycloaddition productions. Addition of NBS to the reaction mixture results in oxidative aromatization to afford pyrrolo [2,1-a] isoquinolines derivatives. The reaction conditions of ethyl 2-(3,4-dihydroisoquinolin-2(1H)-yl)acetate and N-phenyl maleimide were investigated in detail, which include catalyst loading, solvents and bases. The scope and limitations of this reaction were also examined and general compatibility of substrates has been observed. Moreover, the coordination of iron salts with N,N′,N″,N'''-tetrakis(2-pyridylmethyl)- 1,4,8,11-tetraazacyclotetradecane (tpmc) was tested, as a result a typical hydroxo- bridged binuclear complex [Fe2(μ2-OH)(tpmc)](ClO4)3•CH3CH2OH was synthesized. Further studies indicated this complex exhibits no obvious activity in catalyzing C–H oxidation reaction.

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/4390
Collection资源化学研究室
Recommended Citation
GB/T 7714
王宏图. Rh(Ⅱ)催化氧化串联反应合成吡咯并[2,1-a]异喹啉衍生物的研究[D]. 北京. 中国科学院研究生院,2012.
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