乙烯基硒盐参与的串联反应合成1-[1-(胺基)环丙基]酮化合物  

Synthesis of 1-[1-(Amino)cyclopropyl]ketones by Tandem Reaction Involving Vinyl Selenium Salt

作　　者：袁飞 赵艳 郭青松 尹福丹 赖金荣 念倍芳 张明 汤峨[1] Yuan Fei;Zhao Yan;Guo Qingsong;Yin Fudan;Lai Jinrong;Nian Beifang;Zhang Ming;Tang E(Key Laboratory of Medicinal Chemistry for Natural Resource,Ministry of Education,Yunnan University,Kunming 650091)

机构地区：[1]云南大学教育部自然资源药物化学重点实验室,昆明650091

出　　处：《有机化学》2022年第6期1759-1769,共11页Chinese Journal of Organic Chemistry

基　　金：长江学者和创新团队发展计划(No.IRT17R94);国家自然科学基金(No.21762046,22161050);云南科技厅-云南大学“双一流”建设联合基金(No.2018FY001);云南省高校科技创新团队支持计划;云南大学“青年英才”培育计划资助项目~~

摘　　要：发展了一种“一锅法”高效合成1-[1-(胺基)环丙基]酮化合物的新方法.在碱的作用下,β-胺基酮化合物与甲基苯基乙烯基硒四氟硼酸盐发生亲核加成/质子转移/亲核取代脱硒醚的串联反应,以70%~93%的产率得到1-[1-(胺基)环丙基]酮化合物.该方法具有条件温和、操作简单、官能团兼容性良好、区域选择性好等优点.用溴素和肼对副产物甲基苯基硒醚与乙烯基硒盐进行简单处理,就可以制备出合成硒盐的通用原料二苯基二硒醚,继而实现乙烯基硒盐的再生和重复利用,大大地提高了高价硒试剂的利用效率和该方法的工业应用价值.A new one-pot method for the efficient synthesis of 1-(1-(amino)cyclopropyl)ketone compounds has been developed.Under the mediation of 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU),1-(1-(amino)cyclopropyl)ketones were obtained in 70%~93%yields through a reaction sequence of nucleophilic addition/proton migration/nucleophilic substitution and deselenization ofβ-amino ketones and methyl phenyl vinyl selenium tetrafluoroborate.This method features mild reaction conditions,simple experiment operation,good functional group compatibility.Diphenyl diselenide,the general substrate of the selenium salt reagents,can be prepared by the simple treatment of the by-product methyl phenyl selenide with bromine and hydrazine.Therefore,the vinylselenide salts can be regenerated and reused,which improves the utilization of high-valent selenium reagents and improves the industrial application of this method.

关 键 词：高价硒试剂 1-[1-(胺基)环丙基]酮 一锅法 串联反应 

分 类 号：TQ460.1[化学工程—制药化工]