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Reactions of N-trifluoroacetyl trifluoroacetimidoyl chloride with acyclic or cyclic phosphites proceed by the cheletropic 1,4-cycloaddition scheme to form mono- or spirocyclic phosphoranes. The spirophosphorane resulting from the reaction with diethylamino-o- phenylenedioxyphosphite undergoes unusual acid catalyzed stereoselective rearrangement involving ring expansion to afford functionalized cyclic aminophosphonate.
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