{"title":"Efficient Conversion of CO2 and Homopropargylic Amines Promoted by a Stable Noble Metal-Free Cu2O@MOF Heterogeneous Catalyst","authors":"Zhi-Lei Wu, Cang-Hua Zhang, Ling-Jing Guo, Tian-Ding Hu, Ya-Xin Zhang, Bin Zhao","doi":"10.1021/acscatal.4c05376","DOIUrl":null,"url":null,"abstract":"The cyclization reaction of homopropargylic amines and CO<sub>2</sub> to access value-added six-membered heterocycles (1,3-oxazinan-2-ones) is highly desirable yet still a great challenge. Noble metal catalysts are often involved for achieving efficient conversion of this reaction. Herein, one robust porous Fe-based metal–organic framework (MOF) <b>1</b> was prepared, featuring good thermal and solvent/pH stabilities. By encapsulating Cu<sub>2</sub>O nanoparticles inside the cages of <b>1</b>, the resultant non-noble metal catalyst Cu<sub>2</sub>O@<b>1</b> can highly catalyze the cyclization of homopropargylic amines and CO<sub>2</sub> with the turnover number of 10.9, and it can be recycled at least five times. Moreover, this composite MOF catalyst also exhibits rarely catalytic activity for the dopamine derivative and dehydroabietylamine derivative. The reaction mechanism is proposed by nuclear magnetic resonance, <sup>13</sup>C isotope labeling tests, and density functional theory calculations, suggesting that the synergistic catalytic effect between Cu<sub>2</sub>O and 1,8-diazabicyclo[5.4.0]undec-7-ene promotes this reaction, and the protonation process with the energy barrier of 10.6 kcal/mol was the rate-limiting step. In this work, we successfully realized the heterogeneous conversion of CO<sub>2</sub> with homopropargylic amines catalyzed by a noble metal-free catalyst.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3000,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.4c05376","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The cyclization reaction of homopropargylic amines and CO2 to access value-added six-membered heterocycles (1,3-oxazinan-2-ones) is highly desirable yet still a great challenge. Noble metal catalysts are often involved for achieving efficient conversion of this reaction. Herein, one robust porous Fe-based metal–organic framework (MOF) 1 was prepared, featuring good thermal and solvent/pH stabilities. By encapsulating Cu2O nanoparticles inside the cages of 1, the resultant non-noble metal catalyst Cu2O@1 can highly catalyze the cyclization of homopropargylic amines and CO2 with the turnover number of 10.9, and it can be recycled at least five times. Moreover, this composite MOF catalyst also exhibits rarely catalytic activity for the dopamine derivative and dehydroabietylamine derivative. The reaction mechanism is proposed by nuclear magnetic resonance, 13C isotope labeling tests, and density functional theory calculations, suggesting that the synergistic catalytic effect between Cu2O and 1,8-diazabicyclo[5.4.0]undec-7-ene promotes this reaction, and the protonation process with the energy barrier of 10.6 kcal/mol was the rate-limiting step. In this work, we successfully realized the heterogeneous conversion of CO2 with homopropargylic amines catalyzed by a noble metal-free catalyst.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.