TMSN_(3)/NfF:一种有机胺叠氮化试剂的制备和应用

TMSN_(3)/NfF:Preparation and Application of an Organic Amine Azide Reagent

伯胺的重氮转移反应是制备有机叠氮化物的重要手段。高毒、易爆的金属叠氮化物(NaN_(3))一直是制备重氮转移试剂的必需原料。以安全性更高的TMSN_(3)和NfF为原料,制备得到重叠转移试剂NfN_(3),进而开发出一种制备有机叠氮化合物的新方法。该TMSN_(3)/NfF试剂制备有机叠氮的方法,具有良好的底物适用性、官能团兼容性和安全性,且放大至10克级规模,产率无明显下降。所有15个芳香胺、脂肪胺、氨基酸衍生底物都以60%~95%的产率得到了目标叠氮产物。

Diazo-transfer reaction of primary amine is an important synthetic tool for the preparation of organic azides.The highly toxic and explosive metal azide(NaN_(3))is a necessary raw material for the preparation of almost all diazo transfer reagents.Therefore,a new method was developed for the preparation of organic azide compounds by preparation of diazo-transfer reagent NfN_(3) from comparatively safe azide source TMSN_(3) and NfF.This diazo transfer reaction showed wide substrate applicability,good functional group compatibility,safety and the yield had no obvious decrease when scaled up to 10 grams.All 15 aromatic amines,aliphatic amine,and amino acid-derived substrates were transformed to desired azides in 60%~95%yields.