新型水杨酮拼接手性烯胺类化合物的高效合成  

Highly Efficient Synthesis of Novel Chiral Salicyl Enaminone Compounds

作　　者：杨瑶 张磊[1] 黄雄 刘仁明 刘雄利[1] 彭礼军[1] YANG Yao;ZHANG Lei;HUANG Xiong;LIU Ren-ming;LIU Xiong-li;PENG Li-jun(National & Local Joint Engineering Research Center for the Exploition of Homology Resources of Medicine and Food, Guizhou University, Guiyang 550025, China;Yongkang No.2 Middle School, Jinhua 321300, China)

机构地区：[1]贵州大学西南药食两用资源开发利用技术国家地方联合工程研究中心,贵州贵阳550025 [2]永康市第二中学,浙江金华321300

出　　处：《合成化学》2022年第3期227-232,共6页Chinese Journal of Synthetic Chemistry

基　　金：贵大培育项目(202078号)。

摘　　要：以经济易得的色酮-3-甲酸1与手性仲胺2为原料,在无催化剂和室温条件下,以氯仿做溶剂发生Michael加成/脱羧/开环反应,合成了11个未见文献报道的水杨酮拼接手性烯胺类化合物3a~3k,产率72%~91%,其结构经^(1)H NMR,^(13)C NMR和HR-MS(ESI-TOF)表征。进一步通过单晶确定了化合物3a和3i的结构。该方法不需要添加任何催化剂,利用色酮-3-甲酸的高亲电性和手性仲胺中氮原子的高亲核性发生Michael加成反应,生成的手性中间体不稳定发生开环反应,最终得到产物水杨酮拼接手性烯胺类化合物3,可以为天然产物的全合成提供多样性的合成子或者作为催化剂手性配体。Eleven chiral salicyl enaminone compounds 3a~3k were synthesized by Michael addition/decarboxylation/ring opening reaction with economically available chromone-3-formic acid 1 and chiral secondary amine 2 in chloroform as solvent without catalyst and at room temperature.The yields were 72%~91%.Their structures were characterized by ^(1)H NMR,^(13)C NMR and HR-MS(ESI-TOF).The configuration of compounds 3a and 3i was further determined by the single crystal.The method does not need any catalyst,uses the high electrophilicity of chromone-3-formic acid 1 and the nucleophilic property of chiral secondary amine 2 to produce Michael addition reaction,the generated intermediates are unstable,decarboxylation and ring opening reaction to produce the desired chiral salicyl enaminone compounds 3,which can provide a variety of synthons for the complete synthesis of natural products or serve as chiral catalyst ligands.

关 键 词：色酮-3-甲酸 手性仲胺 MICHAEL加成 脱羧 开环反应 合成 

分 类 号：O626.13[理学—有机化学] O623.7[理学—化学]