四炔的芳炔环加成反应简便合成芳胺有机化学.pdfVIP

DOI: 10.6023/cjoc201409032 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 四炔的芳炔环加成反应简便合成芳胺 吴玉芹a 于凉云a 张 奇a 李立冬*,a,b (a 盐城工学院化学与生物工程学院 盐城 224051) (b 安徽师范大学化学与材料科学学院 芜湖 241000) 摘要 芳胺作为一种合成砌块广泛存在于天然产物、医药品及分子材料中. 诸如一些亲核芳香取代、亲电硝化还原、 及过渡金属促进的氨基化合物芳基化作用等作为合成策略在 Caryl—N 键形成领域被长期应用. 本工作在无金属催化条 件下通过四炔的芳炔环加成(Hexadehydro-Diels-Alder, HDDA)反应高效合成了芳胺化合物. 该反应特征表现在无金属 催化、无添加剂、无氧化剂、无导向基团前体, 反应在温和条件下高产率地得到炔官能化二环化合物并表现了优越的 区域选择性. 所合成产物的结构经各种波谱手段表征确证, 其中化合物 3h 的结构还通过X 射线单晶衍射分析确认. 关键词 芳胺; 合成; Caryl—N 偶联; HDDA 反应 Simple Synthesis of Arylamines from Tetraynes via the Hexadehydro-Diels-Alder Reaction Wu, Yuqina Yu, Liangyuna Zhang, Qia Li, Lidong*,a,b a ( School of Chemical and Biological Engineering, Yancheng Institute of Technology, Yancheng 224051) (b College of Chemistry and Materials Science, Anhui Normal University , Wuhu 241000) Abstract Arylamines are widespread in natural products, pharmaceuticals and molecular materials, and are useful synthetic building blocks. From a synthetic standpoint, the formation of Caryl—N bonds has been achieved by classical methods such as nucleophilic aromatic substitution, electrophilic nitration/reduction, or the transition-metal-mediated arylation of amides. This paper describes an efficient method for the synthesis of arylamines by the hexadehydro-Diels-Alder (HDDA) reaction of tetraynes under catalyst-free co