Formal Allylic C(sp <sup>3</sup> )−H Carboxylation With CO <sub>2</sub> via Copper Metallaphotoredox Catalysis
Abstract
ABSTRACT Catalytic carboxylation of ubiquitous C─H bonds with CO 2 has been demonstrated as a sustainable and streamlined pathway to valuable carboxylic acids. However, the catalytic carboxylation of abundant allylic C(sp 3 )─H bonds with CO 2 , which presents a unique opportunity to synthesize structurally diverse 3‐butenoic acids, still remains challenging. Herein, we report the first copper metallaphotoredox‐catalyzed formal allylic C(sp 3 )─H carboxylation with CO 2 , enabling efficient and selective synthesis of 3‐butenoic acids under mild and redox‐neutral conditions. This strategy lies in combining highly reducing photocatalysts to generate alkene radical anion intermediates with copper catalysis to orchestrate regioselective elimination, providing a distinct pathway from traditional allylic C(sp 3 )─H functionalization via forming allyl‐metal intermediates. This method features high atom and step economy, broad substrate scope, good functional group tolerance, facile scalability, and easy access to valuable compounds, including diverse bioactive molecules, natural products, and 13 C‐labeled anti‐inflammatory drug sulindac.
Article Details
Authors (15)
Jun‐Ping Yue
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Huan‐Zhen Li
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Li‐Cai Liu
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Guang‐Rui Liu
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Zu‐Tong Li
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Xin‐Yi Zhang
Faculty of Chemistry Northeast Normal University Changchun China
Wen Wang
Jin‐Cheng Xu
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Lei Song
Hanjiao Chen
Analytical & Testing Center
Xia Jiang
Department of Clinical Neuroscience, The Karolinska Neuroimmunology & Multiple Sclerosis Centre, Centre for Molecular Medicine, Karolinska Institutet
Jian‐Bo Zhu
National Engineering Laboratory of Eco‐Friendly Polymeric Materials (Sichuan) State Key Laboratory of Advanced Polymer Materials College of Chemistry Sichuan University Chengdu P. R. China
Si‐Shun Yan
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Jian‐Heng Ye
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China
Da‐Gang Yu
Key Laboratory of Green Chemistry & Technology of Ministry of Education College of Chemistry Sichuan University Chengdu P. R. China