有机化学 ›› 2019, Vol. 39 ›› Issue (12): 3560-3566.DOI: 10.6023/cjoc201906033 上一篇    下一篇

研究简报

氨甲酰基硅烷作为氨酰基源合成3-羟基-3-杂环丁基甲酰胺衍生物

张鹏鹏, 陈雯雯, 冯花, 陈建新   

  1. 山西师范大学化学与材料科学学院 山西临汾 041004
  • 收稿日期:2019-06-28 修回日期:2019-07-22 出版日期:2019-12-25 发布日期:2019-08-07
  • 通讯作者: 陈建新 E-mail:jjxxcc2002@yahoo.com
  • 基金资助:
    山西省留学回国人员基金(No.0713)、山西省自然科学基金(No.2012011046-9)和山西省自然科学青年基金(No.201701D221033)资助项目.

Synthesis of 3-Hydroxy-3-heterocyclebutylamide Derivatives Using Carbamoylsilanes as an Amide Source

Zhang Pengpeng, Chen Wenwen, Feng Hua, Chen Jianxin   

  1. College of Chemistry and Material Science, Shanxi Normal University, Linfen, Shanxi 041004
  • Received:2019-06-28 Revised:2019-07-22 Online:2019-12-25 Published:2019-08-07
  • Supported by:
    Project supported by the Foundation for Returness Overseas Scientists of Shanxi Province (No. 0713), the Natural Science Foundation of Shanxi Province (No. 2012011046-9), and the Natural Science Youth Foundation of Shanxi Province (No. 201701D221033).

几种氨甲酰基硅烷与四元环氧-3-酮和四元环硫-3-酮在无催化剂甲苯作溶剂的温和条件下,发生亲核加成反应,直接制备了3-羟基-3-杂环丁基酰胺衍生物,收率为56%~85%,为合成含无手性中心的四元杂环药物提供了一种有效途径.通过不同氨甲酰基硅烷的选择,用此方法可合成3-羟基-3-杂环丁基叔酰胺、仲酰胺和伯酰胺衍生物,以及酰氨基带手性中心的3-取代杂环丁基酰胺.通过研究反应的影响因素发现,氨甲酰基硅烷的酰氨基所带基团旳大小是影响反应的重要因素,它既影响反应完成的时间,又影响产物的产率.该反应具有条件温和、副产物少、产物得率高和后处理简单等优点,是有效合成3-羟基-3-杂环丁基甲酰胺的新方法.

关键词: 氨甲酰基硅烷, α-羟基酰胺, 环杂丁基酰胺, 亲核加成, 合成方法

3-Hydroxy-3-heterocyclebutyl amide derivatives were directly synthesized in 56%~85% yields by nucleophilic addition of various carbamoylsilanes to oxetane-3-one or thietane-3-one in toluene under mild and catalyst-free conditions. This method will provide an efficient route for the synthesis of drugs containing four-membered heterocycles which have not additional stereocentres. The procedure can prepare 3-hydroxy-3-heterocyclebutyl tertiary, secondary and primary amides as well as having a stereocentre connecting with nitrogen atom by selecting different carbamoylsilanes. A comparison of the results obtained from reaction of various carbamoylsilanes indicated that the size of group on the amide group was an important factor in the addition reaction, which influenced on both the reaction time and yields. The reaction has the advantages of mild conditions, less by-products, good yield and simple post-treatment, and is a new method for the efficient preparation of 3-hydroxy-3-heterocycle butylamides.

Key words: carbamoylsilane, α-hydroxyamides, heterocyclicbutylamides, nucleophilic addition, synthetic methods