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1,3-共轭烯炔不仅是有机合成的重要中间体,许多天然产物和具有生理活性的化合物的核心骨架都含有共轭烯炔单元,在已有的共轭烯炔的合成方法中钯铜共催化的烯基卤与端炔的Sonogashira偶联反应占据了统治地位.炔卤化合物是一种独特有趣的有机分子,它既能参与类似于端炔的偶联反应,又具有卤苯的过渡金属氧化加成的性能,这些特点使炔卤在构建复杂有机分子中起着重要的作用.我们以Pd(OAc)2为催化剂,K2CO3为碱,在DMF溶剂中实现了末端烯和炔基溴的交叉偶联反应高区域和立体选择性地合成1,3-共轭烯炔,考察了催化剂的种类、碱的种类和温度对反应的影响.研究结果表明:5 mol%Pd(OAc)2,2.5 equiv.K2CO3,在DMF溶剂中,不需要任何配体和添加剂,炔基溴与苯乙烯衍生物于80℃,与贫电子烯烃于室温反应2 h可以高产率得到所需产物,所有化合物的结构用IR,1H NMR,13CNMR,MS,高分辨质谱等方法进行了表征,该偶联反应合成途径简捷、反应条件温和,可为共轭烯炔化合物合成提供简便的途径.
1,3-Conjugated enyne is not only an important intermediate for organic synthesis, but also contains a number of natural products and physiologically active compounds that contain conjugated enyne units. In the conventional synthesis method of conjugated enyne, palladium The copper-catalyzed Sonogashira coupling reaction of alkenyl halides with terminal alkynes dominates. Alkyne halides are a unique and interesting class of organic molecules that participate both in coupling reactions similar to terminal alkynes and halobenzene These characteristics make alkyne halides play an important role in the construction of complex organic molecules.We use Pd (OAc) 2 as catalyst, K2CO3 as base, and the terminal alkene and alkynyl The cross-coupling reaction of bromine with high selectivity and stereoselective synthesis of 1,3-conjugated alkyne, the effects of the type of catalyst, the type of alkali and the temperature on the reaction were investigated.The results showed that: 5 mol% Pd (OAc) 2,2.5 equiv.K2CO3 in DMF solvent without any ligands and additives, alkynyl bromine and styrene derivatives at 80 ℃, with the electron-poor olefins at room temperature for 2 h can be obtained in high yield the desired product, all The structure of the compound was characterized by IR, 1H NMR, 13CNMR, MS, high resolution mass And other methods were used to characterize the coupling reaction is simple synthetic route, mild reaction conditions, may provide an easy way for the synthesis of conjugated enyne compounds.