選擇性催化控制三唑苯甲醯胺進行環外二角七環化反應及環內二角八環化反應，合成6-苯並三唑二氮雜品酮及7-苯並三唑二氮索辛酮

透過取代的乙炔基三唑基苯甲醯胺3-9 (N-methyl-2-(4-phenyl-5-(phenylethynyl)-1H-1,2,3-triazol-1-yl)benzamide)的區域選擇性分子內環化 (intramolecular cyclization)合成新穎的1,2,3-三唑稠合1,5-苯並二氮雜品酮及1,2,3-三唑稠合1,5-苯並二氮索辛酮。該合成法的特點是使用CuI / NBS催化體系，將取代的2-疊氮基苯甲酸酯3-3經過一鍋化反應合成關鍵的中間體5-碘-1,2,3-三唑苯甲酸酯3-5。接著，5-碘-1,2,3-三唑苯甲酸酯中的碘透過Sonogashira Coupling被多種末端炔所取代。最後，經過水解 (hydrolysis)及醯胺化 (amidation)反應後，1,4,5-取代-1,2,3-三唑苯甲醯胺3-9在Pd(PPh3)4/K2CO3或AgOTf/K2CO3條件下，分別進行7-exo-dig及8-endo-dig分子內環化反應得到產率不俗及富有選擇性的1,2,3-三唑稠合-1,5-苯二氮卓酮3-10或1,2,3-三唑稠合-1,5-苯二氮卓辛酮3-11。

關鍵字

環內二角；環外二角；催化；鈀；銀

並列摘要

A regioselective and efficient synthesis of both innovative 1,2,3-triazole-fused-1,5-benzodiazocinones and 1,2,3-triazole-fused-1,5-benzodiazpinones through intramolecular cyclization of substituted ethynyl triazoyl amide were explored. A vital precursor 5-iodo-1,2,3-triazole benzoate was obtained from substituted 2-azido benzoic acid esters in a single step through a Copper-Catalyzed Azide−Alkyne Cycloaddition (CuAAC) reaction using a CuI/NBS catalytic system. A carbon−carbon triple bond was installed through a Sonogashira coupling reaction by kinds of terminal alkynes. The 1,4,5-substituted ethynyl triazoyl benzoate was then underwent hydrolyzation and amidation. Finally, the 1,4,5-substituted ethynyl triazoyl benzamide were cyclized by a Pd(PPh3)4 or AgOTf mediated intramolecular cyclization to aﬀord 7-exo-dig 1,2,3-triazole-fused-1,5-benzodiazpinones or 8-endo-dig 1,2,3-triazole-fused-1,5- benzodiazocinones individually.