Iodine(III)-Catalyzed Rearrangements of Imides: A Versatile Route to α,α-Dialkylated α-Hydroxy Carboxylamides

A tertiary hydroxy group a to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal-free rearrangement of imides triggered by hypervalent lambda(3)-iodane, an easy and selective way to gain access to such a compound class, namely alpha,alpha-disubstituted-alpha-hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent lambda(3)-benziodoxolones are involved in these organocatalytic reactions.