Li Wenjuan, Cheng Huihang, Han Huabo, Li Lu, Liu Xinming, Chu Xianxu, Li Xiaopei
Henan Key Laboratory of Biomolecular Recognition and Sensing, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000, China.
Henan Engineering Research Center of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000, China.
Molecules. 2024 Sep 9;29(17):4266. doi: 10.3390/molecules29174266.
A novel approach for the -alkylation of ketones was developed using Brønsted acid-catalyzed C-C bond cleavage. Both aromatic and aliphatic ketones reacted smoothly with 2-substituted 1,3-diphenylpropane-1,3-diones to afford -alkylation products with high yields and with excellent regioselectivity, in which the 1,3-dicarbonyl group acted as a leaving group in the presence of the catalyst TfOH. Mechanism experiments showed that the -C-C bond cleavage of diketone and the shift of the equilibrium towards the enol formation from ketone are driving forces that induce the desired products.
利用布朗斯特酸催化的碳-碳键裂解，开发了一种新型的酮α-烷基化方法。芳香族和脂肪族酮均可与2-取代的1,3-二苯基丙烷-1,3-二酮顺利反应，以高产率和优异的区域选择性得到α-烷基化产物，其中在催化剂三氟甲磺酸（TfOH）存在下，1,3-二羰基基团作为离去基团。机理实验表明，二酮的α-碳-碳键裂解以及酮向烯醇形成的平衡转移是诱导生成所需产物的驱动力。
