Hypervalent Iodine(III) Reagents with Transferable Primary Amines: Structure and Reactivity on the Electrophilic α-Amination of Stabilized Enolates

A new family of hypervalent iodine reagents containing transferable primary amine groups is described. Benziodoxolone-based reagents were synthesized on the gram-scale through operationally simple reactions in up to quantitative yields. These bench-stable solids were characterized by X-ray analysis and successfully employed in the α-amination of indanone-based β-ketoesters in up to 83% yield. Mechanistic studies indicate a substitution mechanism involving an electrophilic amine.