Palladium-catalyzed direct (het)arylation reactions of strongly electron-withdrawing tricyclic benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and its 4,8-dibromo derivative were studied; the conditions for the selective formation of mono- and bis-aryl derivatives were found. The reaction of 4,8-dibromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) with thiophenes in the presence of palladium acetate as a catalyst and potassium pivalate as a base, depending on the conditions used, selectively gave both mono- and bis-thienylated benzo-bis-thiadiazoles in low to moderate yields; arenes were found to be inactive in these reactions. It was discovered that direct C–H arylation of benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole with bromo(iodo)arenes and -thiophenes in the presence of Pd(OAc)2 and di-tert-butyl(methyl)phosphonium tetrafluoroborate salt is a powerful tool for the selective formation of 4-mono- and 4,8-di(het)arylated benzo-bis-thiadiazoles. Oxidative double C–H hetarylation of benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole with thiophenes in the presence of Pd(OAc)2 and silver (I) oxide in DMSO was successfully employed to prepare bis-thienylbenzo-bis-thiadiazoles in moderate yields.

中文翻译：

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钯催化的苯并[1,2-d:4,5-d']双([1,2,3]噻二唑和4,8-二溴苯并[1,2-d:4, 5-d']双([1,2,3]噻二唑)

钯催化的强吸电子三环苯并[1,2-d:4,5-d']双（[1,2,3]噻二唑）及其4,8-二溴衍生物的直接（杂）芳基化反应研究过；发现了选择性形成单芳基和双芳基衍生物的条件。4,8-二溴苯并[1,2-d:4,5-d']双([1,2,3]噻二唑)与噻吩在乙酸钯为催化剂、新戊酸钾为碱的条件下的反应, 根据所使用的条件, 选择性地以低到中等的收率得到单-和双-噻吩基化的苯并-双-噻二唑; 发现芳烃在这些反应中没有活性。发现苯并 [1,2-d:4,5-d']bis([1,2, 3]噻二唑与溴（碘）芳烃和-噻吩在 Pd(OAc)2 和二叔丁基（甲基）四氟硼酸盐存在下是选择性形成 4-单-和 4,8 的有力工具-二（杂）芳基化苯并双噻二唑。在 Pd(OAc)2 和氧化银 (I) 存在下苯并 [1,2-d:4,5-d'] 双 ([1,2,3] 噻二唑与噻吩的氧化双 C-H 杂芳化反应DMSO 成功地用于以中等收率制备双噻吩基苯并双噻二唑。