Palladium‐Catalyzed Three‐Component Diaryl Sulfone Synthesis Exploiting the Sulfur Dioxide Surrogate DABSO

Abstract

SO(2) effizient: Eine palladiumkatalysierte Dreikomponentenkupplung verknüpft Aryllithiumverbindungen, SO2 (freigesetzt aus DABSO als leicht handhabbare Quelle) und Aryl‐, Heteroaryl‐ oder Alkenyl(pseudo)halogenide unter Bildung einer vielfältigen Sulfonbibliothek. Ein elektronenarmer XantPhos‐Ligand unterbindet den Aryl‐Aryl‐Austausch und ermöglicht hohe Ausbeuten.

New frontiers in the transition-metal-free synthesis of heterocycles from alkynoates: an overview and current status

“…After performing several mechanistic experiments and in line with the literature reports, the authors proposed a possible reaction mechanism which starts with the coordination of arydiazonium cation 167 with DABSO to form the complex 170 via electrostatic interaction. 165 Homolytic cleavage of the N-S bond 166 Due to the widespread applications of sulfone functionalities in organic and medicinal chemistry, [168][169][170][171][172][173][174][175][176][177] the synthesis of organic molecules with these groups remained an attractive pursuit for many research groups. Recently, Wang and coworkers 178 developed a new metal-free approach to construct structurally diverse 3-sulfonated coumarins 180 (Scheme 42).…”

Synthesis of α‐Sulfonyl Ketones through a Salicylic Acid‐Catalyzed Multicomponent Reaction Involving Arylsulfonation and Oxidation

“…[25][26]28,[30][31][36][37][40][41]43] Through the initial work of Willis, Wu, and others, [46][47][48][49][50][51] 1,4diazabicyclo[2.2.2]octane-sulfur dioxide (DABSO) [52] has been demonstrated as a convenient and safe surrogate for sulfur dioxide in radical-mediated arylsulfonylation reactions. [46][47][48][53][54][55][56][57][58] In this regard, Wu and co-workers have developed several methods for the synthesis of α-sulfonyl ketones using DABSO as the sulfonylation reagent, starting from either the reaction of iodoarenes and silyl enol ethers under the activation of UV light (Scheme 1, Eq. 1), [59] the reaction of aryldiazonium salts and 3-arylpropiolic acids under copper catalysis (Scheme 1, Eq.…”

Double SO2 Insertion into 1,7-Diynes Leading to Functionalized Naphtho[1,2-c]thiophene 2,2-dioxides

“…On the other hand, the insertion of sulfur dioxide into molecular skeletons has proven to be a powerful tool for the collection of biologically interesting sulfone-containing structures like sulfones and sulfonamides in a convergent manner . Over the past few years, the pioneering work of the group of Willis has stimulated extensive studies on the insertion of sulfur dioxide with nucleophiles (Nu) and electrophiles (E) for sulfone and sulfonamide syntheses by exploiting bench-stable solid DABCO·(SO 2 ) 2 (DABSO) as the source of sulfur dioxide (Scheme a) . Later, Wu and co-workers reported a three-component reaction of aryldiazonium tetrafluoroborates, DABSO, and aryl propiolates to afford 3-sulfonated coumarins (Scheme b) .…”