Reactions of organoboranes with chloramine-T and its analogues; Synthesis of N-substituted sulphonamides

Electrophilic Amination: The Case of Nitrenoids

“…Smith et al. converted trialkylboranes to the corresponding N ‐tosylamines (Scheme ) 64. Kabalka and co‐workers also found that hydrazoic acid (HN 3 ; 39 ) generated from sodium azide in the presence of 10 % aqueous HCl could also be used to aminate trialkylboranes, whereas only one alkyl group was expected to be transferred (Scheme ) 65…”

Developments in Transition-Metal-Catalyzed Reactions Using Electrophilic Nitrogen Sources

“…The seminal work of the amination of alkylboranes was reported by Brown and co-workers. They later published a stereospe-A wide range of electrophilic nitrogen sources have been developed for the oxidation of alkylboranes to amines, including N-chloroamine, 5b hydroxylamine-O-sulfonic acids, 4a O-mesitylsulfonylhydroxylamine, 6 N-chloro-O-2,4dinitrophenylhydroxylamine, 7 chloramine T, 8 hydrazoic acid, 9 N-chloroalkylamines, 10 sodium N-chlorocarbamates, 11 organic azides, 12 and the lithium enolate of tert-butyl-N-tosyloxycarbamate 13 (Figure 1). Typically only one of the alkyl groups is oxidized to the amine, in contrast to peroxide oxidation of trialkylboranes where all three alkyl groups are oxidized to the corresponding alcohols.…”

Synthesis of N-Arylsulfonamides by a Copper-Catalyzed Reaction of Chloramine-T and Arylboronic Acids at Room Temperature

“…In 1998, Smith and co-workers discovered that chloramine-T reacts with alkylboranes in the absence of a catalyst to give N-alkylsulfonamides. 6 Recently, Chandrasekaran and co-workers found that chloramine-T behaves as an efficient dual nucleophile when vinylcyclopropanes are used as reaction partners in the presence of bromine, leading to [4.4.0] and [4.3.0] bicyclic amidines through tandem ring opening of the vinylcyclopropane and double-nucleophilic addition of chloramine-T; their results also showed that chloramine-T can be regarded as a dual nucleophile when its chlorine atom is removed in the form of BrCl. 7 Theoretically, chloramine-T can also serve as an electrophile, because it readily undergoes oxidative addition at the N-Cl bond in the presence of an appropriate metal catalyst.…”