钯催化立体选择性合成硝基烷类β-碳糖苷  

Pd-Catalyzed Stereoselective Synthesis of Nitroalkyl β-C-Glycosides

作　　者：王兢睿 冯永奎 王能中 黄年玉 姚辉 Wang Jingrui;Feng Yongkui;Wang Nengzhong;Huang Nianyu;Yao Hui(Key Laboratory of Natural Products Research and Development,Key Laboratory of Functional Yeast(China National Light Industry),College of Biological and Pharmaceutical Sciences,China Three Gorges University,Yichang,Hubei 443002)

机构地区：[1]三峡大学生物与制药学院、中国轻工业功能酵母重点实验室、天然产物研究与利用湖北省重点实验室,湖北宜昌443002

出　　处：《有机化学》2023年第9期3216-3225,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(22207063);高等学校学科创新引智计划(111计划);高等学校学科创新引智计划(D20015);湖北省自然科学基金(2022CFB838);湖北省教育厅(D20221204);湖北省教育厅(Q20221212)。

摘　　要：碳糖苷因其优异的生理活性及耐水解/酶解特性, 在医学和生物学领域的研究中受到越来越多的关注, 但合成过程中仍面临着立体选择性的控制等挑战. 报道了一种3,4-O-碳酸酯烯糖和硝基化合物在双乙酰丙酮钯和1,4-双(二苯膦)丁烷(DPPB)配体的催化作用下, 室温反应得到具有高立体选择性的β-碳糖苷的方法, 且已由核磁共振(NMR)、高分辨质谱(HRMS)以及X射线单晶衍射等方法确定目标化合物的结构. 该方法具有广泛的底物范围, 对含吸电子基或供电子基的硝基烷类化合物都有很好的兼容性, 能以高产率得到单一β构型的碳糖苷, 为快速构建碳苷化合物库提供了可靠方法.C-Glycosides have attracted more and more attention in the field of medicine and biology due to their excellent physiological activities and stability to hydrolysis/enzymolysis. However, the challenges of stereoselective control are still high during the synthesis process. In this paper, a method for preparing β-C-glycosides with high stereoselectivity through the reaction of 3,4-O-carbonate-D-galactal and nitroalkane with Pd(acac)2 and 1,4-bis(diphenylphosphino)butane (DPPB) ligand at room temperature has been reported. The structures of the target compounds have been determined by nuclear magnetic resonance spectroscopy (NMR), high-resolution mass spectra (HRMS) and X-ray single crystal diffraction. The method has a wide range of substrates, and has good compatibility for both electron-withdrawing and electron-donating nitroalkanes. Single β-C-glycosides were obtained with high yields, which provide a reliable method for the rapid construction of C-glycoside libraries.

关 键 词：烯糖 立体选择性 半乳糖碳苷 碳糖苷化反应 钯催化 

分 类 号：O629.13[理学—有机化学]