Li Chao, Chen Xiao-Wang, Liao Li-Li, Gui Yong-Yuan, Yang Jing-Wei, Zhang Shuo, Yue Jun-Ping, Zhou Xiangge, Ye Jian-Heng, Lan Yu, Yu Da-Gang
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, 29 Wangjiang Road, Chengdu, 610064, P. R. China.
West China School of Public Health and West China Fourth Hospital, Sichuan University, Chengdu, 610041, P. R. China.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413305. doi: 10.1002/anie.202413305. Epub 2024 Nov 19.
Precise synthesis of carboxylic acids via catalytic carboxylation with CO is highly appealing. Although considerable advancements have been achieved in difunctionalizing carboxylation of unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly in addressing axially chiral alkenes. Herein, we report the first catalytic atroposelective carboxylation of alkynes with CO. A variety of valuable axially chiral carboxylic acids are obtained with good yields and high chemo-, regio-, Z/E and enantio-selectivities. Notably, an unexpected anti-selective carbo-carboxylation is observed in the sp-hybrid carbo-electrophile-initiated reductive carboxylation of alkynes. Mechanistic studies including DFT calculation elucidate the origin of chiral induction and anti-selectivity in vinyl-carboxylation of alkynes.
通过与一氧化碳进行催化羧化反应精确合成羧酸极具吸引力。尽管在不饱和烃的双官能团羧化反应方面已取得了相当大的进展，但不对称变体的发展明显不足，尤其是在处理轴手性烯烃方面。在此，我们报道了首例炔烃与一氧化碳的催化对映选择性羧化反应。通过该反应可以以良好的产率以及高化学、区域、Z/E和对映选择性获得多种有价值的轴手性羧酸。值得注意的是，在炔烃的sp杂化碳亲电试剂引发的还原羧化反应中观察到了意想不到的反式选择性碳羧化反应。包括密度泛函理论计算在内的机理研究阐明了炔烃乙烯基羧化反应中手性诱导和反式选择性的起源。
