钯催化炔丙醇与叔丁基异腈选择性合成吡咯并呋喃衍生物和氨基甲酸酯  

Palladium Catalyzed Selective Synthesis of Pyrrolofuran Derivatives and Carbamates from Propargylic Alcohols and tert⁃Butyl Isonitrile

作　　者：林俊旭 习志威 李志平 王迎春 LIN Junxu;XI Zhiwei;LI Zhiping;WANG Yingchun(College of Chemistry and Chemical Engineering,Hunan Engineering Laboratory for Analyse and Drugs Development of Ethnomedicine in Wuling Mountains,Jishou University,Jishou 416000,China;Power China Zhongnan Engineering Corporation Limited,Changsha 410014,China)

机构地区：[1]吉首大学化学化工学院,武陵山地区民族药解析与创制湖南省工程实验室,吉首416000 [2]中国电建集团中南勘测设计研究院有限公司,长沙410014

出　　处：《高等学校化学学报》2023年第2期47-56,共10页Chemical Journal of Chinese Universities

基　　金：湖南省自然科学基金(批准号:2020jj4499);湖南省教育厅自然科学基金(批准号:20A413);湖南省研究生科研创新项目(批准号:CX20211036)资助.

摘　　要：报道了钯催化下炔丙醇与叔丁基异腈反应高选择性合成吡咯并呋喃衍生物和氨基甲酸酯的新方法.在10%(摩尔分数)Pd(OAc)_(2)与110%(摩尔分数)LiBr存在下,一分子炔丙醇与三分子叔丁基异腈在水的参与下发生“有序的”异腈三重插入反应,以56%~73%的产率高选择性地生成了吡咯并呋喃衍生物;而在10%(摩尔分数)Pd(PPh_(3))_(4)和110%(摩尔分数)K_(3)PO_(4)存在下,一分子炔丙醇与一分子叔丁基异腈在空气中氧气的参与下发生简单氧化偶联反应,以51%~74%的产率生成了氨基甲酸酯.该方法仅通过简单改变钯催化剂与盐的种类就能得到不同产物,且反应选择性高,分别为吡咯并呋喃亚胺衍生物和氨基甲酸酯提供了有吸引力的合成途径.Palladium catalyzed highly selective synthesis of pyrrolofuran derivatives and carbamates from propargy⁃lic alcohols and tert-butyl isonitrile was described.In the presence of 10%(molar fraction)Pd(OAc)_(2) and 110%(molar fraction)LiBr,an“orderly”isonitrile triple insertion reaction occurred between one molecule of propargylic alcohols and three molecules of tert-butyl isonitrile with the participation of water,and pyrrolofuran derivatives were selectively obtained in 56%—73%yields.Whereas in the presence of 10%(molar fraction)Pd(PPh_(3))_(4) and 110%(molar fraction)K_(3)PO_(4),carbamates were exclusively produced in 51%—74%yields via oxidative coupling reaction between a molecule of propargylic alcohols and a molecule of tert-butyl isonitrile with the participation of air(O2).Different products with high selectivity could be obtained by simply changing different kinds of palladium catalyst and salt,and this method provides an attractive synthesis route toward pyrrolofuran derivatives and carbamates,respectively.

关 键 词：钯催化 炔丙醇 叔丁基异腈 选择性合成 

分 类 号：O621.3[理学—有机化学]