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Unusual Chemoselective Rh-II-Catalysed Transformations of alpha-Diazocarbonyl Piperidine Cores

机译:α-重氮羰基哌啶核的不寻常的化学选择性Rh-II催化转化

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摘要

The reactivity of various alpha-diazocarbonyl piperidine scaffolds, characterised by an increased molecular complexity, was tested with various Rh-II catalysts. The structure of the starting reagent is of relevance to the synthetic results. An unexpected dimerisation took place, starting from the simple piperidine scaffold, to give the hexahydrotetrazine ring system. Products derived from a nitrogen ylide intermediate or aromatic substitution (1,3,4,5-tetrahydro-2,5-methanobenzo[c]azepine and 1,2,3,3a-tetrahydrocyclopenta[de]isoquinolin-4(5H)-one rings, respectively) were obtained from tetrahydroisoquinoline derivatives. The chemoselectivity of the reaction could be controlled by the choice of starting reagent, Rh-II catalyst and the reaction conditions. Finally, it was found that the azepino heterocycle could coordinate to the catalyst to give new Rh-II complexes.
机译:用各种Rh-II催化剂测试了以分子复杂性为特征的各种α-重氮羰基哌啶骨架的反应性。起始试剂的结构与合成结果有关。从简单的哌啶骨架开始,发生了意外的二聚反应,得到了六氢四嗪环系统。衍生自氮叶立德中间体或芳族取代基的产品(1,3,4,5-四氢-2,5-甲基苯并[c] a庚因和1,2,3,3a-四氢环戊[de]异喹啉-4(5H)-从四氢异喹啉衍生物获得一个环。反应的化学选择性可以通过选择起始试剂,Rh-II催化剂和反应条件来控制。最终,发现该azepino杂​​环可与该催化剂配位以产生新的Rh-II配合物。

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