Metal‐Free Cross‐Coupling of Arylboronic Acids and Derivatives with DAST‐Type Reagents for Direct Access to Diverse Aromatic Sulfinamides and Sulfonamides

Abstract

We have developed a simple and convenient method for the cross-coupling of arylboronic acids and their derivatives with DAST-type reagents under mild and metal-free conditions to directly afford sulfinamides in moderate to good yields. Moreover, sulfonamides were obtained after a simple oxidation reaction. The reaction mechanism was investigated by (18) O-labeling experiments, and the synthetic utility was demonstrated by the sulfoxidation of natural products.

Transition‐Metal‐Free Cross‐Coupling of Arylsilanes with DAST Reagent: Synthesis of Aromatic Sulfinamides

“…Furthermore, sulfinamides are useful intermediates in several organic transformations. For instance, sulfonamides which are of great importance owing to their medical significance are readily obtained by oxidation of sulfinamides . As a consequence, the efficient approaches to construct C‐S=O bonds have attracted continuous interest in organic synthesis.…”

“…For instance, sulfonamides which are of great importance owing to their medical significance are readily obtained by oxidation of sulfinamides. [3] As a consequence, the efficient approaches to construct C-S=O bonds have attracted continuous interest in organic synthesis. In general, the traditional methods for the construction of sulfinamides are homolytic substitution at the sulfur atom, [4] sulfinic acids, [5] sulfinyl chlorides, [6] sulfinates, [7] and disulfides.…”

“…First, intermediate A was generated from DAST in the presence of trace H 2 O in the solvents or reagents. [3] Substrate 1 a was activated by a fluoride anion which was generated from DAST or HF. Then, the nucleophilic sulfuration [17] of intermediate A afforded the corresponding sulfinamide, and intermediate B [18] was released simultaneously.…”

Electrochemical ipso‐Thiocyanation of Arylboron Compounds

“…However, for thiocyanations, it requires large amounts of copper in combination with an increased partial oxygen pressure . To the best of our knowledge, there are only three examples of metal‐free ipso ‐sulfurations of aryl−boron compounds: The synthesis of diphenyl disulfide and diphenyl sulfide from various phenyl borates using S 8 , S 2 Cl 2 , or (PhSO 2 ) 2 S as sulfur sources, the synthesis of sulfonamides from boronic acids and diethylaminosulfur trifluoride (DAST), and the synthesis of Ph 2 B−SCN, in which formation of PhSCN has been proposed as a side reaction . However, this side product was not isolated.…”

Direct Synthesis of Sulfinamides by the Copper‐Catalyzed Electrophilic Amidation of Sulfenate Anions

“…Recently, Sun developed an efficient pathway through direct activation of tert ‐butyl sulfoxide by NBS under acidic conditions and subsequent reaction with N ‐nucleophiles to access sulfinamides (Scheme a) . Very recently, Shi also disclosed a nice cross‐coupling method for the synthesis of aryl sulfinamides using arylboronic acids and DAST‐type reagents as the starting materials (Scheme b) . With the significance of sulfinamides, there is considerable demand in devising more mild, large scale, convenient and efficient synthetic strategies to afford aryl and alkyl sulfinamides and therefore increase the exploration of sulfinamide chemistry.…”