One-Pot Rhodium-Catalyzed Synthesis of Highly Substituted Quinolines
One-Pot Rhodium-Catalyzed Synthesis of Highly Substituted Quinolines
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一锅法铑催化合成高取代喹啉
DOI：
10.1055/s-0037-1609309
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
P. Richardson
中科院分区：
文献类型：
--
作者：
V. Snieckus;P. Richardson
意义：由重氮化合物分解产生的铑类胡萝卜素物质的合成多功能性已得到充分证实，并且在乙烯基类胡萝卜素铑的情况下尤其得到增强，因为乙烯基可以参与下游转化，通常以一锅法的方式。 Sharma 及其同事此前曾报道过在九元氧杂环化合物的立体选择性合成中使用乙烯基类铑铑（Org. Lett. 2016, 18, 5340）。他们当前工作的最初目标是合成相应的氮杂环化合物。出乎意料的是，通过额外的分子内羟醛脱水序列分离出了三环喹啉。评论：在回流甲苯中，用注射泵将重氮苯甲酸乙烯酯添加到氨基查耳酮以及 (2E)-1-(2-氨基苯基)-3-苯基丙-2-en-1-one 和 Rh2(OAc)4 的混合物中，从而分离出主要化合物，单晶 X 射线结构分析表明该化合物是三环喹啉衍生物。氨基查尔酮上可以耐受一系列取代基，EWG 对反应速率几乎没有不利影响，并且反应性官能团（例如呋喃或其他烯烃）的耐受性良好。当 N-苄基保护的氨基查尔酮经历反应条件时，相应的九元氮杂环被分离出来，尽管产率适中。代表例：O
Significance: The synthetic versatility of rhodium carbenoid species generated by the decomposition of diazo compounds is well established and is particularly enhanced in the case of rhodium vinylcarbenoids because the vinyl group can participate in downstream transformations, often in a one-pot manner. Sharma and co-workers have previously reported on the use of rhodium vinylcarbenoids in the stereoselective synthesis of nine-membered oxacycles (Org. Lett. 2016, 18, 5340). The initial goal of their current work was the synthesis of the corresponding azacycles. Unexpectedly, tricyclic quinolines were isolated through an additional intramolecular aldol–dehydration sequence. Comment: Syringe-pump addition of vinyl diazobenzoate to the aminochalcone and a mixture of (2E)-1-(2-aminophenyl)-3-phenylprop-2-en-1-one and Rh2(OAc)4 in refluxing toluene led to the isolation of a major compound shown to be a tricyclic quinoline derivative by single-crystal X-ray structure analysis. A range of substituents were tolerated on the aminochalcone, with EWGs showing little adverse effect on the rate of the reaction, and reactive functionalities such as furans or an additional olefin being well tolerated. When an N-benzyl-protected aminochalcone was subjected to the reaction conditions, the corresponding ninemembered azacycle was isolated, albeit in modest yield. Representative examples: O