烷烃/烷基芳烃与一氧化碳的自由基羰基化研究进展  

Research progress on radical carbonylation of alkanes or alkylarenes with carbon monoxide

作　　者：孙巧 殷爱华 徐元 随山红 董岩 王昌盛 张东顺[4] 郭凯[2] SUN Qiao;YIN Aihua;XU Yuan;SUI Shanhong;DONG Yan;WANG Changsheng;ZHANG Dongshun;GUO Kai(College of Food Science and Light Industry,Nanjing Tech University,Nanjing 211816,Jiangsu,China;College of Biotechnology and Pharmaceutical Engineering,Nanjing Tech University,Nanjing 211816,Jiangsu,China;School of Chemistry,Chemical Engineering and Biotechnology,Nanyang Technological University,637371,Singapore;SINOPEC Beijing Research Institute of Chemical Industry,Beijing 100013,China)

机构地区：[1]南京工业大学食品与轻工学院,江苏南京211816 [2]南京工业大学生物与制药工程学院,江苏南京211816 [3]南洋理工大学化学化工与生物技术学院,新加坡637371 [4]中石化(北京)化工研究院,北京100013

出　　处：《低碳化学与化工》2025年第4期1-18,共18页Low-Carbon Chemistry and Chemical Engineering

基　　金：江苏省青年基金(BK20220326);江苏省特聘教授项目(54908022);南京工业大学科研启动金(39808137,39829124);南京工业大学食品与轻工学院学科基金(30929000);中国石化委托技术开发项目(202410038,202410043)。

摘　　要：羰基官能团广泛存在于天然产物、医药、农药和高分子材料结构中,开发新颖、高效以及绿色的羰基化方法是合成化学领域最热门的研究课题之一。烷烃和烷基芳烃作为重要的能源和化工原料,广泛存在于石油和天然气中。从简单烷烃(如环戊烷、环己烷)或烷基芳烃(如甲苯、乙苯)出发,通过C—H键的直接羰基化高选择性地制备高附加值羰基衍生物是一个充满挑战且富有前景的研究领域。在众多羰基供体中,一氧化碳(CO)因具有原子效率100%和价格低廉的优点,是使用最为广泛的羰基化试剂。基于过去近15年来烷烃、烷基芳烃与CO的自由基羰基化领域取得的重要成果,综述了以过氧类化合物或光催化剂作为引发剂,H_(2)O、H_(2)O_(2)、醇、芳基亚磺酸酯、偶氮二羧酸酯、胺、亚胺、酰胺和烯烃等作为反应试剂,制备羧酸、酯、酰胺类(包括酰肼、酰胺、α-酮酰胺、β-内酰胺和酰亚胺)和酮类(包括手性胺基酮)高附加值羰基衍生物的研究进展。然后,根据羰基化反应的产物类型进行了分类阐述,并对反应的底物适用范围以及典型的反应机理进行了讨论。最后,对烷烃和烷基芳烃自由基羰基化领域所面临的挑战和机遇进行了分析和展望。Carbonyl functional groups are widely present in the structures of natural products,pharmaceuticals,agrochemicals,and polymer materials.The development of innovative,efficient and green carbonylation methods is one of the hottest research topics in the field of synthetic chemistry.As important energies and chemical raw materials,alkanes and alkylarenes are widely prevalent in petroleum and natural gas.The highly selective preparation of high value-added carbonyl derivatives through direct carbonylation of C—H bonds,starting from simple alkanes(e.g.,cyclopentane,cyclohexane)or alkylarenes(e.g.,toluene,ethylbenzene),represents a challenging and promising research area.Among the diverse carbonyl donors,carbon monoxide(CO)is the most extensively utilized carbonylation reagent owing to its 100%atomic efficiency and cost-effectiveness.Based on the significant achievements in the field of radical carbonylation of alkanes or alkylarenes with carbon monoxide over the past fifteen years,the progress on the synthesis of high value-added carbonyl derivatives such as acids,esters,amides(including acyl hydrazides,amides,α-ketoamides,β-lactams and imides)and ketones(including chiral amino ketones)by utilizing peroxide-type compounds or photocatalysts as the initiators,and H_(2)O,H_(2)O_(2),alcohols,arylsulfinates,azodicarboxylates,amines,imines,amides or olefins as the reaction partners was summarized.Then,the product types of carbonylation reactions were classified and explained,and the substrate scopes and typical reaction mechanisms were discussed.Finally,the challenges and opportunities in the field of radical carbonylation of alkanes and alkylarenes were analyzed and prospected.

关 键 词：烷烃 烷基芳烃 一氧化碳 自由基羰基化 高附加值羰基衍生物 

分 类 号：TQ216[化学工程—有机化工] O622.5[理学—有机化学]