Ligand‐Free Pd/Cu‐Catalyzed Aminosulfonylation of Aryl Iodides for Direct Sulfonamide Syntheses

Abstract

Scheme1.Transition-metal-catalyzed sulfinations: a) Pd II -catalyzed sulfonylation of aryl boronic acids for the synthesis of sulfinates; b) Pd-catalyzed sulfonylation of aryl halidesleading to ammonium sulfinates; c) Cu-catalyzed electrophilic amination of sulfinates; d) One-pot Pd/Cu-catalyzed aminosulfonylation of boronic acids;e)Ligand-free Pd/Cu-catalyzed aminosulfonylation of aryl iodides.[a]

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

“…Alternatively, preformed reagents such as O -benzoyl hydroxylamines can be used in combination with copper catalysis to achieve similar transformations. 495−497…”

“…N -Chloroamines, generated in situ by the combination of bleach with the appropriate amines, have been used for the one-pot, two-step synthesis of sulfonamides ( 801 ), through the intermediacy of either metal or ammonium sulfinates (Scheme ). Alternatively, preformed reagents such as O -benzoyl hydroxylamines can be used in combination with copper catalysis to achieve similar transformations. − …”

Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges

“…238−240 Cooperative Pd/Cu catalysis without a ligand is used in a one-pot synthesis of arylsulfonamides in the reaction of aryl iodides, DABSO, and O-benzoyl hydroxylamines (Scheme 36, A). 241 This reaction successfully proceeds when replacing aryl iodide with arylboronic acid (Scheme 36, B). 242 It should be noted that the preparation of such an important class of sulfonamides, which includes known drugs, can be carried out via an electrophilic amination of sodium sulfinates catalyzed by CuBr 2 (Scheme 36, C).…”

“…Cooperative Pd/Cu catalysis without a ligand is used in a one-pot synthesis of arylsulfonamides in the reaction of aryl iodides, DABSO, and O- benzoyl hydroxylamines (Scheme , A) . This reaction successfully proceeds when replacing aryl iodide with arylboronic acid (Scheme , B) .…”

DABSO as a SO2 gas surrogate in the synthesis of organic structures

“…In another research study, CuBr 2 was employed to attach an amine group to the sulfinate intermediate. 42 The research group of Willis could develop a Cu(II)-catalyzed one-pot sulfonamide 14 synthesis by treating boronic acids 19 with DABSO and secondary amines (Scheme 11). This method shows a broad scope and great functional group tolerance in terms of the used boronic acids and amines.…”