Silver‐Catalyzed Denitrative Sulfonylation of β‐Nitrostyrenes: A Conve­nient Approach to (E)‐Vinyl Sulfones

Abstract

The first utilization of β‐nitrostyrenes (readily available by the Henry reaction) for a highly stereoselective, convenient, and catalytic synthesis of (E)‐vinyl sulfones at room temperature was investigated. The protocol involves efficient silver‐catalyzed denitrative radical cross‐coupling of β‐nitrostyrenes and sodium sulfinates by using potassium persulfate as an additive to complete the catalytic cycle.

N‐Iodosuccinimide as Bifunctional Reagent in (E)‐Selective C(sp2)−H Sulfonylation of Styrenes

“…( E )‐1‐Bromo‐4‐(2‐(phenylsulfonyl)vinyl)benzene (3 ob) : R f =0.5 (20% ethyl acetate in hexane); white solid; yield 93% (98 mg); mp 103–105 °C (lit . 104–107 °C); 1 H NMR (700 MHz, CDCl 3 ) δ 7.95 (d, J =7.6 Hz, 2H), 7.67‐7.60 (m, 2H), 7.56 (t, J =7.6 Hz, 2H), 7.53 (d, J =8.2 Hz, 2H), 7.35 (d, J =8.2 Hz, 2H), 6.85 (d, J =15.4 Hz, 1H); 13 C NMR (175 MHz, CDCl 3 ) δ 141.2, 140.6, 133.7, 132.5, 131.4, 130.1, 129.6, 128.1, 127.9, 125.8.…”

“…Over the past decades, many classical methods to synthesize vinyl sulfones are reported, which are mainly based on Knoevenagel condensation, olefination reactions like Peterson, Wittig and Horner‐Wadsworth‐Emmons (HWE) reactions . Besides, there are reports available for vinyl sulfone synthesis like Pd/Cu/Fe catalyzed cross coupling reaction of vinyl halide, terminal epoxides, vinyl tosylates, β ‐nitro styrene, vinyl boronic acids, vinyl triflates, propiolic acid, alkene, etc . Recently, Jiang and coworkers have described silver catalyzed synthesis of vinyl sulfone (Scheme c) .…”

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

“…At the same time, the Yadav and Chen groups independently employed the denitrative regioselective sulfonylation of β-nitrostyrenes with sodium sulfinates via a radical cross-coupling pathway ( Scheme 121 ). 183,184 Yadav and co-workers 183 developed for the first time, a silver-catalyzed denitrative-sulfonylation of a wide range of β-nitrostyrenes with different aryl/heteraoryl/alkyl-derived sulfinates under the influence of K 2 S 2 O 8 to give a series of ( E )-vinyl sulfones in moderate to high yields ( Scheme 121A ). Disappointingly, the alkyl-substituted nitroalkene did not yield the desired product under the standard conditions.…”

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

“…The reaction of β-nitroaryl and hetarylalkenes sulfonylation with sodium sulfinates in the presence of AgNO 3 /K 2 S 2 O 8 system was carried out under an inert atmosphere: the formation of the target vinyl sulfones was not observed under air. [136] Various peroxides-based systems were applied for the synthesis of vinyl sulfones from β-nitroalkenes and sulfonyl hydrazides. Thus, the sulfonylation of βnitrostyrenes 240 with sulfonyl hydrazides 241 was conducted with the AIBN/TBHP system in MeCN at 80°C for 10 hours.…”

“…The reaction of β‐nitroaryl and hetarylalkenes sulfonylation with sodium sulfinates in the presence of AgNO 3 /K 2 S 2 O 8 system was carried out under an inert atmosphere: the formation of the target vinyl sulfones was not observed under air [136] …”