【作者】 李丹；

【导师】 戚朝荣； 程海鹰；

【作者基本信息】 华南理工大学 ， 化学工程（专业学位）， 2022， 硕士

【摘要】 钯催化的羰基化反应是有机合成的重要工具,但传统的羰基化反应以有毒可燃的一氧化碳为羰基源,在工业应用中存在安全问题。而二氧化碳是主要的温室气体,同时也是一种理想的可再生碳一资源,具有储量丰富、廉价易得、无毒不燃等优点。发展以二氧化碳替代一氧化碳的羰基化反应,在温和条件下将二氧化碳这一温室气体转化为各种有用的羰基化合物具有重要意义。本论文围绕二氧化碳的活化转化展开研究,通过发展新的催化体系,实现在常压下钯催化卤代芳烃与二氧化碳的还原羰基化反应。主要包括以下两部分工作:（1）钯催化二氧化碳与溴代芳烃的羧基化反应合成芳香羧酸化合物。发现以2mol%的双（二亚芐基丙酮）钯（Pd（dba）₂）为催化剂,2.5 mol%的DPEPhos为配体,苯基硅烷（Ph Si H₃）作为还原剂,三乙胺（NEt₃）为碱,各种溴代芳烃与二氧化碳能顺利在1 atm的压力和60 ^oC温度下反应,以中等至良好的收率生成相应的芳香羧酸化合物。该方法避免利用金属还原剂,具有反应条件温和、官能团兼容性好和底物适用性等优点。（2）钯催化二氧化碳与碘代芳烃的甲酰化反应合成芳香醛化合物。实验发现,以6 mol%的双（三环己基膦）二氯化钯（Pd（PCy₃）₂Cl₂）为催化剂,12 mol%的双（2-吡啶基）甲酮为配体,Ph Si H₃作为还原剂,NEt₃为碱,一系列含给电子基团或吸电子基团的碘代芳烃能与1 atm的二氧化碳在75 ^oC下顺利反应,以中等至良好的收率得到相应的芳香醛化合物。该反应条件温和、底物适用性好,且操作简单,为芳香醛合成提供一条环境友好的途径。更多还原

【Abstract】 Palladium-catalyzed carbonylation reaction is an important tool for organic synthesis.However,the traditional carbonylation reaction uses toxic and combustible carbon monoxide as carbonyl source,which may cause safety problems in industrial application.Carbon dioxide is not only the main greenhouse gas,but also an ideal renewable C1 resource as it is abundant,cheap,nontoxic and nonflammable.Thus,it is of great significance to develop the carbonylation reaction using carbon dioxide instead of carbon monoxide and convert carbon dioxide,a greenhouse gas,into various valuable carbonyl compounds under mild conditions.This paper focuses on the activation and conversion of carbon dioxide.Through the development of new catalytic system,the palladium-catalyzed reductive carbonylations of aryl halides with carbon dioxide under atmospheric pressure could be realized.It mainly includes the following two parts:（1）Palladium-catalyzed carboxylation of aryl bromides with carbon dioxide to synthesize aromatic carboxylic acids.It was found that with 2 mol%Pd（dba）₂ as the catalyst,2.5 mol%DPEPhos as ligand,phenylsilane（Ph Si H₃）as a reducing agent and triethylamine as the base,various aryl bromides can react with carbon dioxide smoothly at the pressure of 1 atm and 60^oC to produce the corresponding aromatic carboxylic acids in moderate to good yields.This method avoids the use of metal reducing agent and has the advantages of mild reaction conditions,good functional group compatibility and substrate applicability.（2）Palladium-catalyzed formylation of aryl iodides with carbon dioxide to synthesize aromatic aldehydes.It was found that using 6 mol%Pd（PCy₃）₂Cl₂ as the catalyst,12 mol%bis（2-pyridyl）ketone as ligand,Ph Si H₃ as a reducing agent and NEt₃ as the base,a series of aryl iodides containing electron-donating or electron-withdrawing groups can react smoothly with carbon dioxide at 75 ^oC under 1 atm of CO₂ pressure,and the corresponding aromatic aldehydes can be obtained in moderate to good yields.The reaction features mild conditions,good substrate scope and simple operation.It provides an environmentally friendly way for the synthesis of aromatic aldehydes.更多还原