钯催化合成噻吩并[2,3-b]噻喃-4-酮类化合物  

Synthesis of Thieno[2,3-b]thiopyran-4-one Derivatives by Palladium Catalysts

作　　者：任传清 季晓晖 张强 曹小燕 季建伟 刘波 REN Chuanqing;JI Xiaohui;ZHANG Qiang;CAO Xiaoyan;JI Jianwei;LIU Bo(Shaanxi Key Laboratory of Catalysis,School of Chemical&Environmental Science,Shaanxi University of Technology,Hanzhong 723000,China)

机构地区：[1]陕西理工大学化学与环境科学学院,陕西省催化基础与应用重点实验室,汉中723000

出　　处：《高等学校化学学报》2024年第5期64-70,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22101165);陕西省教育厅重点实验室项目(批准号:23JS002)资助。

摘　　要：噻吩并[2,3-b]噻喃骨架化合物是一类广泛存在于天然产物中的重要有机分子,也是一类重要的生物活性分子.本文以1,6-二取代基-4-(1,3-二硫戊环-2-亚基)-己烯-5-炔-3-酮类化合物为原料,通过钯催化环合反应合成了一系列噻吩并[2,3-b]噻喃-4-酮类化合物.通过实验筛选的最佳条件如下:以摩尔分数为30%的Pd(OAc)2作为催化剂,采用1.0mmol的底物和1.2mmolK2CO3,在DMF溶剂中,于100℃反应8h,合成了噻吩并[2,3-b]噻喃-4-酮类化合物,产率高达87%,产物结构经核磁共振波谱(1H和13C NMR)及高分辨质谱[HRMS(ESI)]分析确证,并对反应机理进行了探讨.研究结果表明,该方法条件温和、操作安全且收率高.Thieno[2,3-b]thiopyrans are important core structures found in a variety of natural products and other biologically important molecules with a wide range of biological activities.In this work,a series of thieno[2,3-b]thio-pyran-4-one derivatives was constructed from 1,6-disubstituted group-4-(1,3-dithiolan-2-ylidene)-1-en-5-yn-3-one via palladium-catalyzed cycloaddition reactions.Optimization experiments showed that the best experimental condi-tions were as follows:using Pd(OAc)2(30%,molar fraction)as catalyst,the substrate(1.0 mmol)and K2CO3(1.2 mmol)reacted at 100℃for 8 h in N,N-dimethylformamide(DMF),thieno[2,3-b]thiopyran-4-one derivatives were synthesized with a yield of 87%.The composition and structure has been characterized by menas of nuclear magnetic resonance(1H NMR and 13C NMR)and high resolution mass spectrometer(electrospray ionization)[HRMS(ESI)].The mechanism for the reaction was proposed.The menthod had the advantages of mild conditions,safe operation and higher yields.

关 键 词：醋酸钯 催化 噻吩并[2 3-b]噻喃 二硫缩烯酮 

分 类 号：O626.2[理学—有机化学]