Copper-catalyzed direct oxysulfonylation of alkenes with dioxygen and sulfonylhydrazides leading to β-ketosulfones

Abstract

The first copper-catalyzed oxysulfonylation reaction of alkenes with dioxygen and sulfonylhydrazides for the construction of β-ketosulfones has been developed under mild conditions without any ligand or additive.

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“…Radical 7 may follow two possible pathways to form different products. Path A involves the use of sulfinic acid and pyridine and leads to β‐hydroxy sulfones,3h whereas path B employs sodium sulfinate in aqueous media, and this could be a plausible route for the formation of β‐keto sulfones 3 in our case 3e. A study of the detailed mechanism is underway.…”

“…β‐Keto sulfones are attractive synthetic scaffolds owing to their useful biological properties7 and diverse synthetic applications ranging from natural products8 to important organic compounds 9. Consequently, β‐keto sulfones have been described as the target of synthesis in numerous reports 3e,3i,10. Recently, Timoshenko and co‐workers reviewed their methods of synthesis and their chemical properties in addition to the applications of this important class of organic compounds 11.…”

“…Recently, Timoshenko and co‐workers reviewed their methods of synthesis and their chemical properties in addition to the applications of this important class of organic compounds 11. Among the very recent methods for the synthesis of β‐keto sulfones are a copper‐catalyzed direct oxysulfonylation of alkenes with dioxygen and sulfonyl hydrazides reported by Wang et al3e and a dioxygen triggered radical route starting from terminal alkynes developed by Lie et al3i We also recently disclosed a synthesis of β‐keto sulfones by using a AgNO 3 /K 2 S 2 O 8 catalyst system in DMF by oxysulfonylation of alkenes with dioxygen and arenesulfinates10i in contrast to the present work, which is transition‐metal‐free and uses stoichiometric amounts of reagents in water. The previously reported methods suffer from multistep processes, reagents in large stoichiometric ratios, and the use of transition metals, high temperatures, and non‐green solvents.…”

Synthesis of β-keto-sulfones via metal-free TBAI/TBHP mediated oxidative cross-coupling of vinyl acetates with sulfonylhydrazides

“…3 Commonly, β-ketosulfones are prepared by the alkylation of sodium sulfinates with α-halo-ketones or α-tosyloxy ketones, which suffer from some limitations such as the pre-functionalized materials, relatively complicated or harsh reaction conditions and undesired byproducts. 4 For recent years, much effort has been devoted to expanding radical sulfonylation of carbon−carbon multiple bonds for constructing β-keto-sulfones and these methods have been well developed by the group of Lipshutz, 5 Yadav, 6 Wang, 7 Huang, 8 Lei, 9 and Loh. 10 However, despite some progress has been made, the problem of the potential metal contamination are still involved in most of these transformations, which will limit their massive applications in the pharmaceutical industry.…”

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

“…[2] The addition of sulfonyl radicals to unsaturated systemss uch as alkenes and alkynes represents ap articularly useful approacht osuch compounds. [3] With this strategy,v arious sulfonyl radicals, generatedf rom sulfonyl hydrazides, [4] dimethyls ulfoxide, [5] sulfinates, [6] sulfinic acids, [7] and thiophenols, [8] etc. have been successfully employed in these radical reactions to furnish keto sulfones.…”