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Research Article pubs.acs.org/acscatalysis Copper(I)@Carbon-Catalyzed Carboxylation of Terminal Alkynes with CO2 at Atmospheric Pressure Bing Yu,? Jia-Ning Xie,? Chun-Lai Zhong,? Wei Li,*,? and Liang-Nian He*,? ?State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, and ?Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071, People’s Republic of China *S Supporting Information ABSTRACT: Activated carbon supported CuBr was found to be an e?cient catalyst for the carboxylation of terminal alkynes under atmospheric pressure of CO2 using ethylene carbonate as solvent at 80 °C for only 2 h, as veri?ed with 13CO2. Various terminal alkynes could react smoothly with CO2 and organic halides under the reaction conditions to a?ord the corresponding carboxylic esters. In addition, the catalyst can be easily recovered and reused at least ?ve times without signi?cant loss of activity. KEYWORDS: carbon dioxide, alkynes, carboxylation, copper, heterogeneous catalysis ■ INTRODUCTION Carbon dioxide is an abundant, ubiquitous, cheap, and nontoxic gas in nature. However, the concentration of CO2 in the atmosphere has risen sharply since the Industrial Revolution, primarily due to the combustion of fossils fuels.1 As the principal greenhouse gas thought to be causing global warming, CO2 has gained considerable attention in recent years. Consequently, a number of methods for CO2 capture and storage (CCS) have been developed for mitigation of carbon emission.2?6 On the other hand, catalytic transformation of CO2 into value-added compounds can be regarded as a desirable alternative to CCS.7 In fact, CO2 transformation on a large scale is still limited today due to its inherent thermodynamic stability and kinetic inertness. Traditionally, this challenge can be surm