Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, ON, L2S 3A1, Canada.
Department of Chemistry & Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, ON, L8S 4L8, Canada.
Chemistry. 2020 Jan 2;26(1):206-211. doi: 10.1002/chem.201903719. Epub 2019 Nov 12.
Reaction of NacNacAl (NacNac=[DippNC(Me)CHC(Me)NDipp] ) with one equivalent of benzophenone affords a ketylate species NacNacAl(η (C,O)-OCPh ) that undergoes easy cyclization reactions with unsaturated substrates. The scope of substrates included benzophenone, aldimine (PhNC(Ph)H), quinoline, phenyl nitrile, trimethylsilyl azide, and a saturated cyclic thiourea. The latter substrate reacted by an unusual C-N cleavage that left the C=S functionality intact. The new products were characterized by NMR spectroscopy and X-ray diffraction analysis.
NacNacAl(NacNac=[DippNC(Me)CHC(Me)NDipp])与等当量的二苯甲酮反应生成酮化物 NacNacAl(η(C,O)-OCPh),该酮化物易与不饱和底物发生环化反应。底物的范围包括二苯甲酮、亚胺(PhNC(Ph)H)、喹啉、苯腈、三甲基硅基叠氮化物和饱和环状硫脲。后一种底物发生了不寻常的 C-N 断裂反应,C=S 官能团保持完整。新产物通过 NMR 光谱和 X 射线衍射分析进行了表征。