Hydroalumination of Ketenimines and Subsequent Reactions with Heterocumulenes: Synthesis of Unsaturated Amide Derivatives and 1,3-Diimines
作者:Xing Jin、Matthias Willeke、Ralph Lucchesi、Constantin-Gabriel Daniliuc、Roland Fröhlich、Birgit Wibbeling、Werner Uhl、Ernst-Ulrich Würthwein
DOI:10.1021/acs.joc.5b00466
日期:2015.6.19
treatment of the hydroaluminated ketenimines 5 with various heterocumulenes like carbodiimides, isocycanates, isothiocyanates and ketenimines as electrophiles and subsequent hydrolytic workup resulted in novel enamine derived amide species in case of N-attack (sterically less hindered ketenimines) under formation of a new C–N-bond or in 1,3-diimines by C–C-bond-formation in case of bulky substituents at
使用氢化二异丁基铝将一系列不同取代的酮亚胺1进行水光处理。对于空间拥塞的酮亚胺1a,通过X射线晶体学(化合物5a)证明了C═N键的优选的氢铝化。用碳二亚胺,异氰酸酯,异硫氰酸酯和酮亚胺等各种杂枯烯类作为亲电子体对氢化铝的酮亚胺5进行原位处理,然后进行水解处理,生成了新的烯胺衍生的酰胺物种(如果存在N)-在新的C–N键形成或1,3-二亚胺通过C–C键形成的情况下发生攻击(空间受阻较少的酮亚胺),如果在酮亚胺-氮原子上存在大的取代基。此外,与多于1当量的亲电试剂的多米诺反应或通过随后添加两种不同的亲电试剂的多米诺反应是可能的,并导致缩二脲类型的多官能酰胺衍生物,否则其不易获得。