基于光氧化反应的1-苯甲酰基-3,4-二氢异喹啉类生物碱Nelumstemine和Longifolonine的首次全合成  

First Total Syntheses of 1-Benzoyl-3,4-dihydroisoquinoline Alkaloids Nelumstemine and Longifolonine Based on the Photo-oxidation

作　　者：黄永康 解文静 罗永强 范琪琦 朱星亮 刘世领 施小新 Huang Yongkang;Xie Wenjing;Luo Yongqiang;Fan Qiqi;Zhu Xingliang;Liu Shiling;Shi Xiaoxin(Engineering Research Center of Pharmaceutical Process Chemistry of the Ministry of Education,School of Pharmacy,East China University of Science and Technology,Shanghai 200237;Qingping Pharmaceutical Company Limited,Shanghai 201710)

机构地区：[1]华东理工大学药学院制药工程与过程化学教育部工程研究中心,上海200237 [2]青平药业有限公司,上海201710

出　　处：《有机化学》2020年第5期1281-1289,共9页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.20972048,20172015)资助项目.

摘　　要：研究了1-苯甲酰基-3,4-二氢异喹啉生物碱的一条新的合成路线.以3,4-二甲氧基苯甲醛为起始原料,通过6步反应,以50%的总收率首次全合成得到生物碱Nelumstemine;另外,以香兰醛为起始原料,通过9步反应,以35%的总收率首次全合成得到生物碱Longifolonine.上述全合成的关键步骤为,可见光照射下1-苄基-3,4-二氢异喹啉在室温下被空气氧化为1-苯甲酰基-3,4-二氢异喹啉的反应,并对此温和的光化学反应进行了详细研究.A novel synthetic route for the total syntheses of 1-benzoyl-3,4-dihydroisoquinoline alkaloids was developed.Nelumstemine was synthesized for the first time via 6 steps in 50%overall yield starting from 3,4-dimethoxybenzaldehyde,and longifolonine was also synthesized for the first time via 9 steps in 35%overall yield starting from vanillin.The key step of these total syntheses is photo-oxidation of 1-benzyl-3,4-dihydroisoquinolines to 1-benzoyl-3,4-dihydroisoquinolines by air under visible-light irradiation at room temperature.The unique mild photo-oxidation of 1-benzyl-3,4-dihydro-isoquinolines has been studied in detail.

关 键 词：苯甲酰基二氢异喹啉生物碱 光氧化 Nelumstemine Longifolonine 

分 类 号：O629.3[理学—有机化学]