Sigmatropic Experimental Procedures

Experimental Procedure 4.2.6. Oxonium Ylide Formation and 2,3-Sigmatropic Rearrangement Ethyl 2,5-Dimethoxy-4-pentenoate [1264]... 

This procedure illustrates a general method for the preparation of rearranged allylic amines from allylic alcohols.2,3 The method is experimentally simple and has been used to prepare a variety of allylic prim-, sec-, and tert-carbonyl amines as illustrated in Table I. The only limitation encountered so far is a competing ionic elimination reaction which becomes important for tri-chloroacetimidic esters of 3-substituted-2-cyclohexen-l-ols.3 4 The rearrangement is formulated as a concerted [3,3]-sigmatropic rearrangement on the basis of its stereo- and regiospecificity3,5 which are... 

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