铑催化1-磺酰基-1,2,3-三氮唑与β-二酮合成2-羰基吡咯的反应研究

发布时间：2018-06-29 21:07

本文选题：铑催化 + 1-磺酰基-1　；参考：《浙江理工大学》2017年硕士论文

【摘要】：过渡金属卡宾在有机合成中是一类重要的活泼中间体,在有机合成中具有广泛的应用价值。过渡金属卡宾一般是由过渡金属催化重氮化合物的分解获得。2008年,Fokin和Gevorgyan等人发现1-磺酰基-1,2,3-三氮唑可以经过Dimroth重排反应,促使其五元环开环生成α-亚胺重氮化合物。1-磺酰基-1,2,3-三氮唑可以方便地通过铜催化炔烃与叠氮化合物获得。随后1-磺酰基-1,2,3-三氮唑被广泛地用作重氮化合物前体物质,以过渡金属铑为催化剂生成α-亚胺铑卡宾中间体。由于α-亚胺铑卡宾中间体高度活泼的化学性质,它可以经历一系列化学转化,例如:经历环丙化反应生成三元环化合物、碳氢键插入、氧氢键插入、氮氢键插入以及一些别的类型的金属卡宾反应等。本论文主要研究了通过铑催化1-磺酰基-1,2,3-三氮唑与β-二酮的反应对2-羰基吡咯化合物的合成。通过对反应条件的筛选优化,确定了在5 mol%Rh2(piv)4为催化剂,1,2-二氯乙烷为溶剂,氮气保护下回流,1.5当量的1-磺酰基-1,2,3-三氮唑与β-二酮化合物均能以中等到优秀的产率合成2-羰基吡咯化合物。大多数三氮唑与β-二酮均能参与反应生成预期的目标产物,并且该反应的官能团兼容性较好,如甲氧基、溴原子、氟原子、氯原子等。当使用苯甲酰丙酮及其衍生物作为反应底物时,目标产物有较好的区域选择性。第一次使用羰基取代的烯醇来捕获α-亚胺铑卡宾的方法合成吡咯为吡咯类化合物的合成提供了更好的便利。
[Abstract]:Transition metal carbene is an important class of active intermediates in organic synthesis and has wide application value in organic synthesis. Transition metal carbene is generally obtained from the transition metal-catalyzed decomposition of diazo compounds. In 2008, Fokin and Gevorgyan et al found that 1-sulfonyl-1-triazole can undergo a Dimroth rearrangement reaction. The 伪 -imide diazo compound. 1-sulfonyl-1 triazole can be easily obtained by copper catalyzed alkynes and azide compounds. Subsequently, 1-sulfonyl-1-triazole was widely used as the precursor of diazo compounds, and the transition metal rhodium was used as catalyst to form 伪 -imine rhodium carbene intermediate. Because of its highly active chemical properties, the 伪 -imine rhodium carbene intermediate can undergo a series of chemical transformations, such as the formation of ternary ring compounds through cyclization, the insertion of hydrocarbon bonds, and the insertion of oxygen and hydrogen bonds. Nitrogen-hydrogen bond insertion and some other types of metal carbene reaction. In this paper, the synthesis of 2-carbonyl pyrrole compounds catalyzed by rhodium was studied. Through the selection and optimization of reaction conditions, it was determined that 5 mol Rh2 (piv) _ 4 was used as catalyst and dichloroethane as solvent. 2-carbonyl pyrrole compounds can be synthesized by refluxing 1. 5 equivalent 1. 5 sulfonyl-2-triazolium and 尾-diketones in medium to excellent yields under nitrogen protection. Most triazoles and 尾 -diketones can participate in the reaction to produce the desired target products, and the functional group compatibility of the reaction is good, such as methoxy, bromine, fluorine, chlorine atoms and so on. When benzoyl acetone and its derivatives are used as substrates, the target product has better regioselectivity. The synthesis of pyrrole by capturing 伪 -imine rhodium carbene with carbonyl substituted enols for the first time provides a better convenience for the synthesis of pyrrole compounds.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626.13

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