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Cite this: DOI: 10.1039/c3ob42522c Received 17th December 2013, Accepted 21st January 2014 DOI: 10.1039/c3ob42522c

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Copper-catalyzed highly selective direct hydrosulfonylation of alkynes with arylsulfinic acids leading to vinyl sulfones Wei Wei,a,b Jinli Li,a,b Daoshan Yang,a,b Jiangwei Wen,a,b Yueting Jiao,a,b Jinmao Youa,b,c and Hua Wang*a,b

A novel Cu-catalyzed direct hydrosulfonylation of alkynes with arylsulfinic acids for the synthesis of (E)-vinyl sulfones has been realized under mild conditions with 100% atom efficiency. The present protocol provides an attractive approach to various vinyl sulfones in good to excellent yields, with the advantages of operation simplicity, atom economy, and high stereo- and regioselectivities.

Transition-metal-catalyzed direct addition of H-heteroatom compounds to carbon–carbon unsaturated triple bonds is one of the most straightforward and powerful tools for the construction of alkenyl heteroatom compounds because of its advantages in terms of synthetic efficiency and atom economy.1 Over the past several decades, considerable efforts have been made in this area and some important alkenyl heteroatom compounds, such as phosphonates,2 boronates,3 selenides,4 sulfides,5 and nitrogen-6 and oxygen-containing7 products, have been obtained via the catalytic addition reaction of alkynes. Nevertheless, there is still a great demand for the development of a new and selective catalytic system to offer other important alkenyl heteroatom compounds such as vinyl sulfones. Herein, we report a novel and efficient coppercatalyzed direct hydrosulfonylation of alkynes with arylsulfinic acids for the construction of vinyl sulfones in a one-pot procedure with 100% atom efficiency (eqn (1)).


As extremely valuable alkenyl heteroatom compounds, vinyl sulfones have increasingly attracted synthetic pursuit of chemists, since they can serve as key structural motifs of many a

The Key Laboratory of Life-Organic Analysis, Qufu Normal University, Qufu 273165, China. E-mail: [email protected] b Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, Qufu Normal University, Qufu 273165, China c Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Xining 810001, PR China

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biologically active compounds8 and versatile building blocks for various organic transformations.9 Generally, vinyl sulfones are prepared by Knoevenagel condensation of aromatic aldehydes with sulfonylacetic acids,10 Wittig reaction,11 Horner– Emmons reaction of carbonyl compounds with sulfonyl phosphoranes,12 and β-elimination of selenosulfones or halosulfones,13 in which the desired products were usually formed in a mixture of isomers. A number of alternative methods towards vinyl sulfones synthesis have also been developed such as the oxidation of vinyl sulfides with stoichiometric oxidants,14 the cross-coupling of sulfinate salts with vinyl triflates, vinyl bromides, or alkenyl boronic acids with Cu or Pd catalysts,15 the addition of ArSO2X (X = I, Cl, SePh, HgCl, ONO2, etc.) to alkenes followed by β-elimination,16 and the addition of ArSO2X (X = I, Cl, etc.), sodium sulfinates or 1,2-bis( phenylsulfonyl)ethane to alkynes.17 However, most of these methods suffer from some limitations such as inaccessible starting materials, tedious procedures, relatively harsh reaction conditions, lack of atom economy, or the generation of large amounts of unwanted byproducts. Therefore, the development of mild, convenient, highly-selective and especially atomeconomic, environmentally friendly, and resource efficient methods to afford vinyl sulfones is still highly desirable. The present method of direct addition of arylsulfinic acids to alkynes is realized under mild conditions by employing simple and cheap copper salts as the catalyst, which provides a variety of vinyl sulfones in good to excellent yields and high regio- and stereoselectivity. To the best of our knowledge, this method is the first example of transition-metal-catalyzed direct synthesis of vinyl sulfones from simple and readily available materials with complete atom economy, and does not require the use of any ligand or additive. Initially, the reaction of phenylacetylene 1a with benzenesulfinic acid 2a was performed to examine the catalytic activity of various transition metal complexes including Ru, Pd, Ag, Cu, Fe, Co, Ni, In and Zn salts in DME at 60 °C under N2. As shown in Table 1, among the above metal catalysts screened (entries 1–13), copper salts especially Cu(OAc)2 were found to

Org. Biomol. Chem.

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Communication Table 1

Organic & Biomolecular Chemistry

Optimization of the reaction conditionsa

Published on 22 January 2014. Downloaded by Lomonosov Moscow State University on 17/02/2014 08:31:30.

Table 2 acidsa,b




Yieldb (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

RuCl3 Pd(OAc)2 In(OAc)3 AgNO3 NiCl2 ZnBr2 Co(OAc)2 FeBr3 CuBr2 CuCl2 CuI Cu(OTf)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 Cu(OAc)2 —


0 0 0 0 Trace Trace Trace

Copper-catalyzed highly selective direct hydrosulfonylation of alkynes with arylsulfinic acids leading to vinyl sulfones.

A novel Cu-catalyzed direct hydrosulfonylation of alkynes with arylsulfinic acids for the synthesis of (E)-vinyl sulfones has been realized under mild...
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