Epoxy amines, Payne rearrangement

Epoxy-3-alcohols can be derived from 2,3-epoxy-1-alcohols by the base-catalyzed Payne rearrangement as illustrated in step d of Figure 6A.4 [59,64], The rearrangement is completely stereospecific but, because it is reversible, it usually results in an equilibrium mixture of the two epoxy alcohols for which the relative proportions are structure-dependent. Practical synthetic applications of this rearrangement therefore depend on methods that will shift the equilibrium completely in the direction desired. Nucleophiles such as thiolates and amines are... 

Payne reaction. Recent methodology takes advantage of the same anchimeric activity in optically active 2,3-epoxy sulfides and 2,3-epoxy amines (82 and 85), whereby treatment with Lewis acid induces rearrangement to the corresponding thiiranium and aziridinium ions (83 and 86) as reactive intermediates which react efficiently with a variety of nitrogen-based nucleophiles to give functionalized hydroxy sulfides (84) or hydroxy amines (87) <97SL11>. 

Scheme 10.3 Aza-Payne rearrangement of representative 2,3-epoxy amines.

Aziridine rings constitute a vital sub-structure of biologically active molecules. This renders the synthesis of such compounds through aza-Payne rearrangement of aziridinemethanols 28 and 2,3-epoxy amines 29 of much interest in connection with the synthesis of bioactive compounds. 

Several epoxy amines have been synthesized via aza-Payne rearrangement of the respective 2,3-aziridin-l-ols. These epoxy amines (70, 72) can serve as synthons for the construction of enantiomerically pure nitrogen heterocycles. 

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