Phosphorus in organic synthesis. The tanigawa reaction revisited as a method for converting alcohols to tertiary amines
作者:Paul Frøyen、Jan Skramstad
DOI:10.1016/s0040-4039(98)01316-1
日期:1998.8
temperatures. A mechanistic scheme implying initial amine exchange between 1 and the added amine leading to the N,N-dimethyl analog 5 is suggested. An improved synthesis where the reactive intermediate 5 is formed in situ from triphenylphosphine, carbon tetrachloride and HNR3R4 is described.
相反,早期观察,Ñ甲基Ñ -phenylaminotriphenylphosphonium碘化1(的Murahashi试剂)不与醇和伯或仲胺反应在温和的条件(80℃)下,得到仲胺或叔胺。但是,该反应可以在较高的温度下成功进行。提出了一种机械方案,该方案暗示1与添加的胺之间的初始胺交换,从而导致N,N-二甲基类似物5。改进的合成方法,其中反应性中间体5由三苯基膦,四氯化碳和HNR 3 R 4原位形成 描述。