On the mechanism of the rearrangement of N-aryl α,α-dichloroketimines with lithium aluminium hydride†

Experimental evidence is provided that the rearrangement of N-aryl α,α-dichloroketimines with lithium aluminium hydride in ether, observed as a competitive reaction during the stereospecific synthesis of cis-aziridines, proceeds via consecutive transformation of α-chloroaziridines into azirinium chlorides and α-imidoylcarbenium ions, the latter being trapped by chloride anion to afford β-chloroenamines, which furnish rearranged anilines on treatment with lithium aluminium hydride.

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