Phospholidines incorporating a β N-sulfonylaminoalcohol moiety: first observed selectivity of phosphorus heterocycle aminolysis in the presence of water
作者:Frédéric Dujols、Laurence Marty、Michel Mulliez
DOI:10.1039/b415285a
日期:——
Eleven 2-oxo or 2-thioxo 3-sulfonyl 1,3,2-oxazaphospholidines were synthesized in one step by condensing P(IV) dichlorides with N-sulfonyl-ethanolamines, or -aminothexylalcohols or -ortho-aminophenols. These compounds, in contrast to all other phosphorus heterocycles studied so far, reacted easily with amines, sometimes selectively in the presence of water, leading to the corresponding amides. The results are rationalized by the involvement of the additionâelimination mechanism of phosphorylation with direct collapse of the primary zwitterionic intermediate formed by the amine attack on phosphorus
通过将P(IV)二氯化物与N-磺酰乙醇胺、-氨基六醇或-邻氨基酚缩合,一步合成了十一种2-氧或2-硫氧的3-磺酰基1,3,2-氧氮杂磷环化合物。这些化合物与迄今为止研究的所有其他磷杂环化合物相比,容易与胺反应,有时在水存在的情况下选择性反应,生成相应的酰胺。结果可以通过磷酸化的加成-消除机制来解释,其中在胺攻击磷产生的初级双性离子中间体直接崩溃。