基于氨甲酰基硅烷的β-硝基酰胺衍生物的合成  

Synthesis ofβ-Nitroamide Derivatives Based on Carbamoylsilane

作　　者：李俊飞[1] 韩宇玲 刘艳红 陈建新[1] Li Junfei;Han Yuling;Liu Yanhong;Chen Jianxin(College of Chemistry and Material Science,Shanxi Normal University,Taiyuan 030031)

机构地区：[1]山西师范大学化学与材料科学学院,太原030031

出　　处：《有机化学》2022年第11期3880-3889,共10页Chinese Journal of Organic Chemistry

基　　金：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);山西省1331工程和山西师范大学有机化学优质课程(No.2019YZKC-13)资助项目。

摘　　要：用氨甲酰基硅烷作氨甲酰基源,对α-硝基-2-烯酸乙酯进行直接氨酰基化反应,在不加催化剂温和条件下,可以53%~96%的分离收率得到β-硝基酰胺衍生物.此方法底物(或官能团)适用范围广,在双键上可连接脂肪烃基、芳香烃基、杂芳香烃基和不饱和芳香烃基.通过不同结构的氨甲酰基硅烷的选择,此方法可合成β-硝基叔酰胺和甲氧甲基保护的仲酰胺衍生物.该合成方法具有反应条件温和、产物收率较高、副产物较少、立体选择性较强以及后处理容易等优点,既是一种制备β-硝基酰胺衍生物的新方法,也是进一步合成具有潜在应用价值的β-氨基酰胺的新方法.Using carbamoylsilane as an carbamoyl source,the direct aminocarbonylation ofα-nitro-2-enoic acid ethyl ester affordedβ-nitroamide derivatives in 53%~96%separation yields under mild conditions without use of catalysts.The protocol has a wide range of substrates(or functional groups),tolerated a nitroalkenes bearing different groups on the C=C bond such as aliphatic group,aryl,hetero aryl and unsaturated aryl.This procedure allows the preparation of variousβ-nitroamides includingβ-nitro tertiary amide derivatives and methoxymethyl-protectingβ-nitro secondary amide derivatives by the selection of various carbamoylsilanes.The synthesis method has the advantages of mild reaction conditions,good to excellent yields,less by-products,strong stereoselectivity and easy post-processing.It is a new method for preparingβ-nitroamide derivatives and then synthesizingβ-aminoamides with potential application value.

关 键 词：亲核加成 氨甲酰基硅烷 β-硝基烯烃 氨酰化 β-硝基酰胺 

分 类 号：O623.626[理学—有机化学]