Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives

Abstract

A diverse chemoselective insertion reaction of sulfoxonium ylides and thiosulfonates under transition-metal-free conditions is developed, which successfully affords 1,4-diketone compounds, arylthiosulfoxide-ylides, and β-keto thiosulfones, respectively. The nucleophilic addition of two molecular sulfoxonium ylides to construct sulfone-substituted 1,4-dione compounds is the highlight of this work.

Asymmetric transformations from sulfoxonium ylides

“…The synthesis of a-keto, a 0 -thioaryl sulfoxonium ylides (86) can be accomplished by exposing cyclohexyl-keto sulfoxonium ylides to the presence of thiosulfonates and 1,10-phenanthroline, via a radical insertion reaction. 131 This reaction can also provide the selenium-substituted sulfoxonium ylide (87) from phenylbenzenesulfonoselenoate in a 44% yield (Scheme 12E). Homocoupling of the keto sulfoxonium ylides in the presence of a copper catalyst in aerobic conditions provides the a,a,b-tricarbonyl sulfoxonium ylides (88).…”

Visible-Light-Induced Radical Cascade Reaction of 1-Allyl-2-ethynylbenzoimidazoles with Thiosulfonates to Assemble Thiosulfonylated Pyrrolo[1,2-a]benzimidazoles

“…When alkynyl bromides or 1,1-dibromo-1-alkenes are employed as substrates, couplings with thiosulfonates also gave ( E )-(β)-arylsulfonylvinyl sulfides in good yields (Scheme c,d) . Wang’s group reported a tandem radical addition of sulfoxonium ylides with thiosulfonates to offer 1,1-thiosulfonylated acetophenones (Scheme e) . Despite the great breakthrough in the development of thiosulfonylation reactions, the reported methods are still limited to the additions with simple alkenes or alkynes.…”

Annulation of CF3–Imidoyl Sulfoxonium Ylides with 1,3-Dicarbonyl Compounds: Access to 1,2,3-Trisubstituted 5-Trifluoromethylpyrroles

“…On the basis of the control experiments and literature reports, a plausible reaction mechanism is shown in Scheme . Initially, the reaction of 1,3-dicarbonyl compound 1 with LiBr generates enolate A , which serves as a nucleophile to react with intermediate B to give intermediate C .…”

“…On the contrary, the insertion of the sulfoxonium ylide-derived carbine into electron-deficient C­(sp 3 )–H bonds is still unknown. With our ongoing interest in sulfoxonium ylide chemistry, we wondered whether it is possible for the TM-free C-alkylation of sufficiently acidic methylene compounds to proceed through the nucleophilic substitution of carbanions to sulfoxonium ylides . Thus CF 3 -containing imidoyl sulfoxonium ylides (TFISYs) were synthesized for the first time, which were proved to be more reactive than their aryl counterparts .…”