Michael addition reactions of cyclanones with acrylamides: Producing 2-carbamoylethyl derivatives or ene-lactams
Michael addition reactions of cyclanones with acrylamides: Producing 2-carbamoylethyl derivatives or ene-lactams
复制标题
环烷酮与丙烯酰胺的迈克尔加成反应：生产 2-氨基甲酰乙基衍生物或烯-内酰胺
DOI：
10.1007/s11426-008-0095-3
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发表时间：
2008-11-01
期刊：
影响因子：
--
通讯作者：
Lang MeiDong
中科院分区：
文献类型：
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作者：
Dai WeiFeng;Wang ChaoHua;Lang MeiDong
Michael加成反应中所用的亲电烯烃中的吸电子基团（EWG）几乎只有CO2 R、CN、COR、NO2和SO2 Ph。酰胺（CONR 1 R2）也是典型的吸电子基团，在有机合成中有着重要的作用，但在Michael加成反应中作为亲电烯烃的吸电子基团却很少。本工作中，在自由基抑制剂存在下，成功地进行了丙烯酰胺及其衍生物与环酮的Michael反应。酰胺基团在制备优选的产物中起关键作用。N-取代丙烯酰胺（包括N-单取代和N，N-二取代）与环己酮（CHn）反应可生成预期的2-氨基甲酰乙基衍生物，而丙烯酰胺与环己酮反应只生成烯-内酰胺。环酮对产物也有影响，环酮环的大小影响反应产率，α-取代基决定异构烯-内酰胺的比例。
The electron-withdrawing groups (EWGs) in the electrophilic alkenes employed in the Michael addition reaction are almost only CO2R, CN, COR, NO2, and SO2Ph. Although amides (CONR1R2) are also typical electron-withdrawing groups and are of great importance in organic synthesis, they are scarcely employed as the EWGs of the electrophilic alkenes in the Michael addition reaction. In this work, the Michael reactions of acrylamide and its derivatives with cyclanones were successfully carried out in the presence of enough radical inhibitors. The amide groups play a key role in producing the preferred products. TheN-substituted acrylamides, includingN-monosubstituted andN,N-disubstituted acrylamides could react with cyclohexanone (CHn) to give the expected 2-carbamoylethyl derivatives; however, acrylamide reacting with cyclohexanone only produced ene-lactam. Cyclanones also have effects on the products, while the ring size of cyclanones influences the reaction yield and the α-substituent decides the ratio of resulting isomeric ene-lactams.