THE AZA-PAYNE REARRANGEMENT : A SYNTHETICALLY VALUABLE EQUILIBRATION
THE AZA-PAYNE REARRANGEMENT : A SYNTHETICALLY VALUABLE EQUILIBRATION
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DOI：
10.1039/a827145z
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发表时间：
1998
影响因子：
46.2
通讯作者：
T. Ibuka
中科院分区：
文献类型：
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作者：
T. Ibuka
以光学活性形式合成的N-活化的2-氮丙啶甲醇与叔丁醇钾（ButOK）、氢化钾（KH）或氢化钠（NaH）在接近0 °C下在常见的非质子溶剂如四氢呋喃（THF）、甲苯或THF-HMPA的混合溶剂中进行氮杂-Payne重排，然后在低温下淬灭，以高产率得到相应的环氧磺酰胺。通过碱处理2-氮丙啶甲醇产生的阴离子反应中间体，容易地以一锅法与各种亲核试剂如有机铜试剂、硫醇和三甲基甲硅烷基氰化物反应，以良好的产率产生光学活性的相应官能化的1，2-氨基醇。在将2，3-环氧胺在-78 °C下暴露于在THF和正己烷的混合溶剂中的ButOK和BuLi（超强碱）的等摩尔混合物时，平衡仅朝向羟基氮丙啶形成方向。
An aza-Payne rearrangement of N-activated 2-aziridinemethanols, synthesized in an optically active form, with potassium tert-butoxide (ButOK), potassium hydride (KH), or sodium hydride (NaH) at near 0 °C in common aprotic solvents such as tetrahydrofuran (THF), toluene, or a mixed solvent of THF–HMPA followed by quenching at low temperature gives the corresponding epoxy sulfonamides in high yields. The anionic reaction intermediates, generated by treatment of 2-aziridinemethanols with a base, react readily in a one-pot manner with a variety of nucleophiles such as organocopper reagents, thiols, and trimethylsilyl cyanide to yield the optically active corresponding functionalized 1,2-amino alcohols in good yields. Upon exposure of 2,3-epoxy amines to an equimolar mixture of ButOK and BuLi (super base) in a mixed solvent of THF and n-hexane at –78 °C, the equilibrium lies exclusively toward the hydroxyaziridine forming direction.