Organic & Biomolecular Chemistry View Article Online

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

COMMUNICATION

Cite this: DOI: 10.1039/c3ob42522c Received 17th December 2013, Accepted 21st January 2014 DOI: 10.1039/c3ob42522c www.rsc.org/obc

View Journal

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)).

ð1Þ

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

This journal is © The Royal Society of Chemistry 2014

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.

View Article Online

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

Entry

Catalyst

Solvent

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 —

DME DME DME DME DME DME DME DME DME DME DME DME DME THF 1,4-Dioxane Toluene DMSO CH3OH CH3CN H2O DME DME DME

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...
204KB Sizes 0 Downloads 0 Views

Recommend Documents


Hydrosulfonylation Reaction with Arenesulfonyl Chlorides and Tetrahydrofuran: Conversion of Terminal Alkynes into Cyclopentylmethyl Sulfones.
An efficient and simple radical chain reaction to convert terminal alkynes into arenesulfonylmethylcyclopentanes is described. The reaction involves a radical addition-translocation-cyclization process and necessitates solely the use of readily avail

Selective oxygenation of alkynes: a direct approach to diketones and vinyl acetate.
Arylalkynes can be converted into α-diketones with the use of a copper catalyst, and also be transformed into vinyl acetates under metal-free conditions, both in the presence of PhI(OAc)2 as an oxidant at room temperature. A series of substituted α-d

Regioselective synthesis of vinyl halides, vinyl sulfones, and alkynes: a tandem intermolecular nucleophilic and electrophilic vinylation of tosylhydrazones.
A diazo species is trapped in an intermolecular fashion by two independent ion species in tandem at the carbene center to install an electrophile and a nucleophile on the same carbon. This metal-free concept, which is unprecedented, has been illustra

Coupling of carboxylic acids with internal alkynes by supported ruthenium catalysts: direct and selective syntheses of multi-substituted phthalide derivatives.
Supported ruthenium catalysts promote coupling of various kinds of aromatic carboxylic acids with internal alkynes, giving the corresponding multi-substituted phthalide derivatives in high yields. The supported Ru catalyst can be recycled at least fi

Direct catalytic olefination of alcohols with sulfones.
The synthesis of terminal, as well as internal, olefins was achieved by the one-step olefination of alcohols with sulfones catalyzed by a ruthenium pincer complex. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressur

Preparation of Alkyl Alkynyl Sulfones and Cyclic Vinyl Sulfones from Alkynyl(aryl)iodonium Salts.
The reaction of alkyl sulfinates with alkynyl(aryl)iodonium salts provides a facile access into otherwise difficult to obtain alkyl alkynyl sulfones and cyclic vinyl sulfones via 1,2-rearrangement or 1,5-CH insertion, respectively. In benzyl sulfinat

PhI(OAc)2 mediated decarboxylative sulfonylation of β-aryl-α,β-unsaturated carboxylic acids: a synthesis of (E)-vinyl sulfones.
A highly efficient metal-free decarboxylative sulfonylation protocol for the preparation of (E)-vinyl sulfones from of β-aryl-α,β-unsaturated carboxylic acids using sodium sulfinates and (diacetoxyiodo)benzene (PhI(OAc)2) was developed. This strategy

A Direct Metal-Free Decarboxylative Sulfono Functionalization (DSF) of Cinnamic Acids to α,β-Unsaturated Phenyl Sulfones.
A metal-free room temperature decarboxylative cross-coupling between cinnamic acids and arylsulfonyl hydrazides has been realized for the first time for the synthesis of (E)-vinyl sulfones. The scope and versatility of the reaction has been demonstra

Air Oxidative Radical Oxysulfurization of Alkynes Leading to α-Thioaldehydes.
Air oxidative radical oxysulfurization of alkynes initiated by 0.5 mol % tert-butyl hydroperoxide with arylthiols is described. The reaction proceeded at room temperature in the presence of 5% mol water to afford selective α-thioaldehydes.

Perfluoroalkanesulfonamide organocatalysts for asymmetric conjugate additions of branched aldehydes to vinyl sulfones.
Asymmetric conjugate additions of branched aldehydes to vinyl sulfones promoted by sulfonamide organocatalyst 6 or 7 have been developed, allowing facile synthesis of the corresponding adducts with all-carbon quaternary stereocenters in excellent yie