Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, P. R. China.
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, 400030, P. R. China.
Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202301892. doi: 10.1002/anie.202301892. Epub 2023 May 3.
Carboxylation of easily available alkenes with CO is highly important to afford value-added carboxylic acids. Although dicarboxylation of activated alkenes, especially 1,3-dienes, has been widely investigated, the challenging dicarboxylation of unactivated 1,n-dienes (n>3) with CO remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO via electrochemistry, affording valuable dicarboxylic acids. Control experiments and DFT calculations support the single electron transfer (SET) reduction of CO to its radical anion, which is followed by sluggish radical addition to unactivated alkenes, SET reduction of unstabilized alkyl radicals to carbanions and nucleophilic attack on CO to give desired products. This reaction features mild reaction conditions, broad substrate scope, facile derivations of products and promising application in polymer chemistry.
用 CO 将易得的烯烃羧化为有价值的羧酸是非常重要的。尽管活化烯烃的双羧化，特别是 1,3-二烯，已经得到了广泛的研究，但 CO 对未活化的 1,n-二烯（n>3）的挑战性双羧化仍未得到探索。在此，我们通过电化学报告了首例未活化的缺电子二烯与 CO 的双羧化反应，得到了有价值的二羧酸。控制实验和 DFT 计算支持 CO 通过单电子转移（SET）还原为其自由基阴离子，随后是缓慢的自由基对未活化烯烃的加成、未稳定的烷基自由基通过 SET 还原为碳负离子以及亲核进攻 CO 生成所需产物。该反应具有温和的反应条件、广泛的底物范围、产物易于衍生化以及在聚合物化学中有很好的应用前景。
