Silver(I)‐Promoted Radical Sulfonylation of Allyl/Propargyl Alcohols: Efficient Synthesis of γ‐Keto Sulfones

Abstract

An efficient Ag CO -promoted sulfonylation of allyl/propargyl alcohols with sodium sulfinates has been developed. The reaction tolerates a wide range of functional groups to deliver γ-keto sulfones in high yields (up to 93 %). Propargyl alcohols furnished trimerization product 1,3,5-triaroylbenzenes in the presence of sodium methanesulfinate under the standard conditions. A mechanism involving a sulfonyl radical was suggested.

Palladium-Catalyzed Aerobic Oxidative Coupling of Allylic Alcohols with Anilines in the Synthesis of Nitrogen Heterocycles

“…Based on the previous reports and our observations, , a plausible reaction pathway is proposed in Scheme , which involves the initial oxidation of allyl alcohols to enones, followed by aza-Michael addition to afford the desired products. Coordination of the allylic alcohol to the catalyst to form complex B is followed by deprotonation to form Pd–alkoxide complex C and a β-hydride elimination to form the enone.…”

“…This method has advantages in accessing β-aryl carbonyl compounds because it avoids the use of highly electrophilic agents such as vinyl ketones and alkyl halides. Notable works by the groups of Sigman, Jiang, Lei, and Kommu, among others, have made considerable contributions to this field. − Transition-metal-mediated oxidation of alcohols to carbonyl compounds has revolutionized the approaches in the organic chemistry, thereby making alcohols important building blocks in synthesis . Palladium-catalyzed oxidation of alcohols has witnessed important advancements, and alcohols are now widely used as efficient alternatives to carbonyl compounds.…”

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds

“…Bi and co-workers described the mechanistically interesting Ag 2 CO 3 -mediated sulfonylation of various allyl/propargyl alcohols with sodium sulfinates to synthesize γ-keto sulfones ( Scheme 94 ). 152 A variety of electron-donating or electron-withdrawing groups on the benzene of propargyl alcohols readily reacted with sulfinate salts to afford the desired vinyl sulfones in high to excellent yields. Similarly, a series of arylallyl alcohols resulted in a smooth conversion with various sulfinates to form the corresponding γ-keto sulfones in high yields.…”

Oxidative Sulfonylation of Multiple Carbon‐Carbon bonds with Sulfonyl Hydrazides, Sulfinic Acids and their Salts

“…Under these conditions, ketovinyl sulfones 149 were obtained from the corresponding propargyl alcohols 148 in 30-92% yields (Scheme 69b). [88] In the first step of the process, sulfonyl radical A is generated from sodium sulfinate 145 under the action of Ag(I). Then, this radical is added to silver acetylenide B to give vinyl radical intermediate C, which is isomerized into D and undergoes hydrogen atom abstraction resulting in E. Finally, proton quenching of E delivers the target product 149 (Scheme 70).…”

“…Thus, the reaction of aryl allyl alcohols 146 with sodium sulfinates 145 in the presence of Ag 2 CO 3 in toluene led to the formation of γ‐ketosulfones 147 in 73–93% yields (Scheme 69a). Under these conditions, ketovinyl sulfones 149 were obtained from the corresponding propargyl alcohols 148 in 30–92% yields (Scheme 69b) [88] . In the first step of the process, sulfonyl radical A is generated from sodium sulfinate 145 under the action of Ag(I).…”