Base-Promoted Deconstructive Reaction of Exocyclic 1,3-Dicarbonyls for Accessing Hydrazonylated 1,n-Dicarbonyls and Its Biological Evaluation  

利用碱促进环外1,3-二羰化合物的解构反应合成腙化的1,n-二羰化合物及其生物活性检测

作　　者：Li Ping Zhang Yin Yang Zi-Qi Hao Wen-Juan Jiang Bo 李平;张寅;杨子琪;郝文娟;姜波(河南医学高等专科学校医学系,郑州451191;江苏师范大学化学与材料科学学院,江苏徐州221116)

机构地区：[1]Medical Department,Henan Medical College,Zhengzhou 451191 [2]School of Chemistry&Materials Science,Jiangsu Normal University,Xuzhou,Jiangsu 221116

出　　处：《有机化学》2024年第9期2777-2784,共8页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21971090);河南省重点研发与推广专项(科技攻关)(No.212102310797);河南省软科学研究计划(No.242400410409)资助项目.

摘　　要：A mild base-promoted three-component deconstructive functionalization of exocyclic 1,3-dicarbonyls with aryl diazonium tetrafluoroborates in the presence of alcohols is reported,enabling direct ring-opening of unstrained cyclic ring systems to produce six types of skeletally diverse hydrazonylated 1,n-diesters(e.g.,1,6-,1,7-1,8-,and 1,9-diesters)and 1,n-ketoesters(e.g.,1,6-and 1,7-ketoesters)with good yields,and the latter demonstrated complete(E)-selectivity.The methodology has the potential to be widely used throughout organic synthesis due to the use of easily accessible substrates with different substitution patterns,such as exocyclic 1,3-carbonyls and aryl diazonium tetrafluoroborates,and mild reaction conditions.Preliminary biological evaluation of some compounds,namely their inhibitory effect on human lung cancer cell MSTO-211H,was conducted.The results showed that compounds 3c and 3w exhibited significant inhibitory effects.报道一类温和碱促进的环外1,3-二羰化合物、芳基重氮四氟硼酸盐和醇的三组分解构官能化反应,使无张力环体系能直接开环,以良好收率合成了六种不同骨架的腙化1,n-二酯衍生物(如1,6-、1,7-、1,8-和1,9-二酯)和1,n-酮酯(如1,6-和1,7-酮酯).其中,在形成1,n-酮酯的转化中,该反应展现出优异(E)-选择性.在整个有机合成过程中,该方法具有广泛使用的潜力,因使用了易于获得的具有不同取代形式的底物,如环外1,3-二羰化合物和芳基重氮四氟硼酸盐,以及温和反应条件.对部分化合物的生物活性,即对人肺癌细胞株MSTO-211H的抑制作用,进行了初步检测.结果显示化合物3c和3u展现出较为显著的抑制作用.

关 键 词：deconstructive reaction 1 n-diesters 1 n-ketoesters STEREOSELECTIVITY 

分 类 号：TQ460.1[化学工程—制药化工]