De Kimpe Norbert, De Smaele Dirk, Sakonyi Zsolt
Department of Organic Chemistry, Faculty of Agricultural and Applied Biological Sciences, University of Gent, Coupure Links 653, B-9000 Gent, Belgium.
J Org Chem. 1997 Apr 18;62(8):2448-2452. doi: 10.1021/jo962351v.
A new synthetic route leading to 2-methyleneaziridines has been developed by base-induced 1,2-dehydrobromination of 2-(bromomethyl)aziridines. Several base-solvent pairs did not lead to 2-methyleneaziridines. Only potassium tert-butoxide in tetrahydrofuran afforded 2-methyleneaziridines in competition with the substitution products, i.e. 2-(tert-butoxymethyl)aziridines. Various attempted functionalizations of 1-(arylmethyl)-2-methyleneaziridines failed, but they proved to be excellent substrates for the synthesis of beta-lactam derivatives, i.e. 1-(arylmethyl)-2-iminoazetidines, through ring expansion with azides carrying electron-withdrawing substituents.
通过碱诱导的2-(溴甲基)氮丙啶的1,2-脱溴化反应，开发了一种通往2-亚甲基氮丙啶的新合成路线。几种碱-溶剂组合并未生成2-亚甲基氮丙啶。只有四氢呋喃中的叔丁醇钾在生成取代产物（即2-(叔丁氧基甲基)氮丙啶）的竞争反应中生成了2-亚甲基氮丙啶。1-(芳基甲基)-2-亚甲基氮丙啶的各种官能化尝试均告失败，但事实证明它们是通过与带有吸电子取代基的叠氮化物进行扩环反应来合成β-内酰胺衍生物（即1-(芳基甲基)-2-亚氨基氮杂环丁烷）的优良底物。
