Electrochemical Ring-Opening Dicarboxylation of Strained Carbon–Carbon Single Bonds with CO 2 : Facile Synthesis of Diacids and Derivatization into Polyesters

作者：Li‐Li Liao, Zhe‐Hao Wang, Ke-Gong Cao, Guo‐Quan Sun, Wei Zhang, Chuan‐Kun Ran, Yiwen Li, Li Chen, Guangmei Cao, Da‐Gang Yu · 发表于：Journal of the American Chemical Society · 年份：2022 · DOI：10.1021/jacs.1c12071 · 被引用次数：148 · 研究领域：Carbon dioxide utilization in catalysis、CO2 Reduction Techniques and Catalysts、Catalytic C–H Functionalization Methods

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO 2 has been demonstrated as a promising synthetic method. However, dicarboxylation of C─C single bonds with CO 2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of C─C single bonds in strained rings with CO 2 . Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.