Photochemically-Mediated, Nickel-Catalyzed Synthesis of N-(Hetero)aryl Sulfamate Esters
J Miles Blackburn1, Anastasia L Gant Kanegusuku1, Georgia E Scott1
1Department of Chemistry, Duke University, Box 90346, Durham, North Carolina 27708-0354, United States.
Abstract:
A general method is described for the coupling of (hetero)aryl bromides with O-alkyl sulfamate esters. The protocol relies on catalytic amounts of nickel and photoexcitable iridium complexes and proceeds under visible light irradiation at ambient temperature. This technology engages a broad range of simple and complex O-alkyl sulfamate ester substrates under mild conditions. Furthermore, it is possible to avoid undesirable N-alkylation, which was found to plague palladium-based protocols for N-arylation of O-alkyl sulfamate esters. These investigations represent the first use of sulfamate esters as nucleophiles in transition metal-catalyzed C-N coupling processes.
Related Concept Videos
Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview
Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
Nomenclature of Aryl and Heterocyclic Amines


