A novel carbonylative approach to the synthesis of functionalized 1H-benzo[d]imidazo[1,2-a]imidazoles is presented. The method consists of the oxidative aminocarbonylation of N-substituted-1-(prop-2-yn-1-yl)-1H-benzo[d]imidazol-2-amines, carried out in the presence of secondary nucleophilic amines, to give the corresponding alkynylamide intermediates, followed by in situ conjugated addition and double-bond isomerization, to give 2-(1-alkyl-1H-benzo[d]imidazo[1,2-a]imidazol-2-yl)acetamides. Products were obtained in good to excellent yields (64–96%) and high turnover numbers (192–288 mol of product per mol of catalyst) under relatively mild conditions (100 °C under 20 atm of a 4:1 mixture of CO–air), using a simple catalytic system, consisting of PdI₂ (0.33 mol %) in conjunction with KI (0.33 equiv).

中文翻译：

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碘化钯催化氧化氨基羰基化-杂环化作用的功能化苯并咪唑咪唑

提出了一种新颖的羰基合成方法，用于合成功能化的1 H-苯并[ d ]咪唑并[1,2- a ]咪唑。该方法由在仲亲核胺的存在下进行的N-取代-1-（prop-2-yn-1-yl）-1 H-苯并[ d ]咪唑-2-胺的氧化氨基羰基化反应组成。得到相应的中间体alkynylamide，随后原位偶联加法和双键异构化，以得到2-（1-烷基-1- ħ -苯并[ d ]咪唑并[1,2一]咪唑-2-基）乙酰胺。在相对温和的条件下（100°C，在20 atm的CO- 4：1混合气中，温度为100°C），获得的产品具有良好至极好的收率（64-96％）和高周转率（每摩尔催化剂192-288 mol产品）。空气），使用简单的催化系统，由PdI ₂（0.33 mol％）和KI（0.33当量）组成。