物理化学学报2024，Vol.40Issue(4)：146-166,21.DOI:10.3866/PKU.WHXB202307004
二氧化碳转化为氨基甲酸酯的研究进展
Recent Progress on Conversion of Carbon Dioxide into Carbamates
摘要
Abstract
Carbon dioxide(CO2)serves as one of the major greenhouse gases in the atmosphere.However,it is also abundant,non-toxic,and renewable,making it a valuable one-carbon source.Therefore,converting CO2 into valuable chemicals holds immense significance as an effective approach towards achieving carbon neutrality.Nevertheless,due to CO2's thermodynamic stability and kinetic inertness,its activation and conversion present considerable challenges.Organic carbamates,both cyclic and acyclic,represent a crucial class of bioactive compounds found in various natural products,agricultural chemicals,and pharmaceutically relevant molecules.They are also widely used as essential intermediates in organic synthesis.Unfortunately,traditional methods for preparing organic carbamates often rely on highly toxic phosgene and its derivatives as raw materials,posing serious environmental and safety concerns and limiting practical applications.From a cost-effective and sustainable standpoint,substituting CO2 for phosgene in the synthesis of organic carbamates is highly appealing.In recent decades,numerous new reactions,particularly multicomponent reactions involving CO2 and amines,have emerged,providing efficient methods for constructing diverse and valuable carbamates.Some of these reactions can be conducted under transition-metal-free conditions,utilizing organic and inorganic bases,ionic liquids,or small organic molecules as catalysts or promoters.However,in certain cases,transition-metal catalysts,such as those based on copper,palladium,or silver,are required,especially when the reactions involve activating unsaturated hydrocarbons like alkenes and alkynes.Mechanistically,most of these methods involve in situ generation of nucleophilic CO2-amine adducts,such as carbamate salts or carbamic acids,which then react with other electrophiles or coupling partners to yield the desired carbamates.Notably,recent advancements have led to the successful development of several elegant methods for synthesizing specific types of carbamates using electrocatalysis or photocatalysis,which are not achievable through conventional thermal catalysis.This review comprehensively summarizes the recent progress in the synthesis of organic carbamates using CO2 and amines under various catalytic conditions,including transition metal-free conditions,transition metal-catalysis,electrocatalysis,and photocatalysis.Additionally,the review discusses the challenges and future prospects associated with converting CO2 into organic carbamates.关键词
胺/二氧化碳/氨基甲酸酯/无过渡金属催化/过渡金属催化/电催化/光催化Key words
Amine/Carbon dioxide/Organic carbamate/Transition metal-free catalysis/Transition metal-catalysis/Electrocatalysis/Photocatalysis分类
化学引用本文复制引用
郭艳辉,魏丽,温中林,戚朝荣,江焕峰..二氧化碳转化为氨基甲酸酯的研究进展[J].物理化学学报,2024,40(4):146-166,21.基金项目
The project was supported by the National Key Research and Development Program of China(2022YFB4101800),the National Natural Science Foundation of China(21971073,22271098),the Natural Science Foundation of Guangdong Province,China(2019A1515011468).国家重点研发计划(2022YFB4101800),国家自然科学基金(21971073,22271098),广东省自然科学基金(2019A1515011468)资助项目 （2022YFB4101800）
