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

Diogo L. Poeira, Ana Cláudia R. Negrão, Hélio Faustino, Jaime A. S. Coelho, Clara S. B. Gomes, Pedro M. P. Góis, M. Manuel B. Marques

2022Organic Letters21 citationsDOI

Abstract

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.

Topics & Concepts

Hypervalent moleculeChemistryAminationReagentElectrophileAmine gas treatingElectrophilic aminationYield (engineering)IodineReactivity (psychology)Primary (astronomy)Combinatorial chemistryOrganic chemistrySubstitution reactionCatalysisMaterials scienceAstronomyPhysicsMedicinePathologyMetallurgyAlternative medicineOxidative Organic Chemistry ReactionsSynthesis and Catalytic ReactionsCatalytic C–H Functionalization Methods
Hypervalent Iodine(III) Reagents with Transferable Primary Amines: Structure and Reactivity on the Electrophilic α-Amination of Stabilized Enolates | Litcius