Three-Component Transformation of CO_(2),Propargyl Alcohols and Secondary Amines intoβ-Oxopropylcarbamates Promoted by a Noble Metal-Free Metal–Organic Framework Catalyst  

作　　者：Xiao-Lei Jiang Fang-Yu Ren Ying Shi Yao Xie Sheng-Li Hou Bin Zhao 

机构地区：[1]Department of Chemistry,Key Laboratory of Advanced Energy Material Chemistry(Ministry of Education),MOE,Renewable Energy Conversion and Storage Center(RECAST),Nankai University,Tianjin 300071 [2]College of Chemistry and Chemical Engineering,Yantai University,Yantai 264010

出　　处：《CCS Chemistry》2024年第9期2333-2345,共13页中国化学会会刊（英文）

基　　金：supported by the National Natural Science Foundation of China(grant nos.92161202,21971125,22101138,21625103,and 22121005);the 111 project(grant no.B12015);the Fundamental Research Funds for the Central Universities(grant no.D5000230371).

摘　　要：The three-component reaction of CO_(2),propargyl alcohols,and secondary amines frequently applies noble metal or homogeneous catalysts,therefore it is necessary and important to seek a recyclable catalyst without noble metals for this reaction,despite the multitude of challenges.Herein,a unique framework{[Ce3(Cu4I4)2(CNA)8(DMF)8](NO3)}n(CuCe-CNA)with two kinds of metal cluster nodes[Ce3]and[Cu4I4]was synthesized,displaying high thermal and chemical stabilities.CuCe-CNA-300 was obtained by removing the coordinated DMF molecules with[Ce3]cluster at 300°C,in which more metal sites are exposed and the pores are enlarged,but the three-dimensional framework still remains intact.CuCe-CNA-300 can effectively catalyze the three-component reaction of 2-methyl-3-butyn-2-alcohol,CO_(2),and pyrrolidine toβ-oxopropylcarbamates with a yield of 98%under mild conditions,and the catalytic activity is higher than those of noble metal catalysts.Additionally,CuCe-CNA-300 exhibits high catalytic efficiency for various kinds of propargyl alcohols and secondary amines,and also shows good recyclability.Mechanistic studies suggest that theα-alkylidene cyclic carbonates derived from the cycloaddition of propargyl alcohols and CO_(2) are the intermediates,which further react with secondary amines through ammonolysis reaction to generateβ-oxopropylcarbamates.Importantly,this work may open a new avenue for the one-pot transformation of CO_(2) with two or more components into value-added chemicals activated by noble metal-free metal–organic frameworks catalysts.

关 键 词：three-component reaction CO_(2)conversion metal-organic frameworks noble metal-free catalyst synergistic catalysis 

分 类 号：O62[理学—有机化学]