351-96-2

Upstream product

• 52148-00-2 trans-2-(p-nitrophenyl)ethenesulfonyl chloride 
• 677-25-8 ethylenesulfonyl fluoride 
• 24067-17-2 4-nitrophenylboronic acid 
• 636-98-6 p-nitrobenzene iodide 
• 100-13-0 4-nitrostyrene 

Downstream Products

• 569-45-9 3exo-(4-nitro-phenyl)-norborn-5-ene-2endo-sulfonyl fluoride 
• 5294-57-5 2-(1-(4-nitrophenyl)ethylidene)-1,3-diphenylpropane-1,3-dione 

Relevant academic research and scientific papers

A Synthesis of dual Warhead β-Aryl Ethenesulfonyl Fluorides and One-Pot Reaction to β-Sultams

Herein, we report an operationally simple, ligand- and additive-free oxidative boron-Heck coupling that is compatible with the ethenesulfonyl fluoride functional group. The protocol proceeds at room temperature with chemoselectivity and E-isomer selectivity and offers facile access to a wide range of β-aryl/heteroaryl ethenesulfonyl fluorides from commercial boronic acids. Furthermore, we demonstrate a one-pot click reaction to directly transform the products to aryl-substituted β-sultams.

Gram-Scale Synthesis of β-(Hetero)arylethenesulfonyl Fluorides via a Pd(OAc)2 Catalyzed Oxidative Heck Process with DDQ or AgNO3 as an Oxidant

A practical oxidative Heck reaction between organoboronic acids and ethenesulfonyl fluoride (ESF) is developed. Aryl- and heteroaryl-boronic acids react efficiently and stereoselectively with ESF in the presence of a catalytic amount of Pd(OAc)2 and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) or AgNO3 in AcOH to afford the corresponding E-isomer of β-arylethenesulfonyl fluoride products. The utility of this reaction is exemplified by an expanded scope of 47 examples including N-, O-, and S-containing heteroaromatics, demonstrating chemoselectivity over aryliodides, and gram-scale operation without the requirement for strict anhydrous or oxygen-free conditions. Furthermore, this procedure discriminates against the formation of arylboronic acids homo-coupling byproducts. In addition, the preparation of the first aryl vinylsulfonate polymer, a material with functionalizable Michael acceptor sites, from a starting arylboronic acid is described. (Figure presented.).

Radical Fluorosulfonylation: Accessing Alkenyl Sulfonyl Fluorides from Alkenes

Sulfonyl fluorides have widespread applications in many fields. In particular, their unique biological activity has drawn considerable research interest in the context of chemical biology and drug discovery in the past years. Therefore, new and efficient methods for the synthesis of sulfonyl fluorides are highly in demand. In contrast to extensive studies on FSO2+-type reagents, a radical fluorosulfonylation reaction with a fluorosulfonyl radical (FSO2.) remains elusive so far, probably owing to its instability and difficulty in generation. Herein, the development of the first radical fluorosulfonylation of alkenes based on FSO2 radicals generated under photoredox conditions is reported. This radical approach provides a new and general access to alkenyl sulfonyl fluorides, including structures that would otherwise be challenging to synthesize with previously established cross-coupling methods. Moreover, extension to the late-stage fluorosulfonylation of natural products is also demonstrated.

Converting (E)-(Hetero)arylethanesulfonyl Fluorides to (Z)-(Hetero)arylethanesulfonyl Fluorides Under Light Irradiation

The construction of (Z)-(hetero)arylethenesulfonyl fluorides was achieved utilizing Iridium photoredox catalysis under UV-light irradiation. This protocol provided a diverse range of (Z)-(hetero)arylethenesulfonyl fluorides in moderate to good yields under mild conditions without external additives. The late-stage transformation of the (Z)-(hetero)arylethenesulfonyl fluorides comparing with their E-configuration counterparts was also studied.

Palladium-Catalyzed Fluorosulfonylvinylation of Organic Iodides

A palladium-catalyzed fluorosulfonylvinylation reaction of organic iodides is described. Catalytic Pd(OAc)2 with a stoichiometric amount of silver(I) trifluoroacetate enables the coupling process between either an (hetero)aryl or alkenyl iodide with ethenesulfonyl fluoride (ESF). The method is demonstrated in the successful syntheses of eighty-eight otherwise difficult to access compounds, in up to 99 % yields, including the unprecedented 2-heteroarylethenesulfonyl fluorides and 1,3-dienylsulfonyl fluorides.