Photocatalytic carboxylation of styrenes with CO2 via C=C double bond cleavage
Catalytic cleavage of C=C double bonds in alkenes is highly important to convert feedstocks into high-value compounds.However,these approaches are mainly limited to oxidative cleavage of al-kenes with excess oxidants and redox-neutral alkene metathesis.In contrast,reductive C=C double bond cleavage and functionalization have not been reported.Herein,we report a novel visible-light photoredox-catalyzed carboxylation of styrenes with CO2 via reductive C=C double bond cleavage.The use of dicyclohexylmethylamine as scission reagent is the key to the success.Different from previous homologation reactions with CO2,this protocol enabled exchange of the carbon of styrenes with CO2,affording important aryl acetic acids via C=C double bond cleavage.Moreover,preliminary mechanistic investigation and DFT calculations shed light on the reaction mechanism,disclosing aminomethyl-carboxylation intermediate,benzylic radicals and carbanions as key intermediates in the reaction.
Carbon dioxideVisible-light photoredox catalysisC=C bond cleavageCarboxylationAryl acetic acids
曹可弓、高田宇、廖黎丽、冉川昆、蒋元旭、章炜、周琦、叶剑衡、蓝宇、余达刚
展开 >
四川大学化学学院,绿色化学与技术教育部重点实验室,四川成都 610064
重庆大学化学化工学院,理论与计算化学重庆市重点实验室,重庆 400044
四川大学华西公共卫生学院,华西第四医院,四川成都 610041
郑州大学化学学院,绿色催化中心,河南郑州 450001
南开大学元素有机化学国家重点实验室,天津 300071
展开 >
二氧化碳 可见光催化 C=C键裂解 羧基化 芳基乙酸
Fundamental Research Funds for the Central Universities.国家自然科学基金Fundamental Research Funds for the Central Universities.国家自然科学基金Fundamental Research Funds for the Central Universities.国家自然科学基金四川大学基础研究基金中国博士后面上基金中央高校基本科研业务费
万方数据
