Elsevier

Tetrahedron

Volume 65, Issue 50, 12 December 2009, Pages 10383-10389
Tetrahedron

Amberlyst-15: an efficient and reusable catalyst for the Friedel–Crafts reactions of activated arenes and heteroarenes with α-amido sulfones

https://doi.org/10.1016/j.tet.2009.10.044Get rights and content

Abstract

The heterogeneous Amberlyst-15 catalyst displays efficient catalytic properties for the Friedel–Crafts reactions between an activated arenes or heteroarenes and α-amido sulfones. Various α-amido sulfones on treatment with 1,2,4-trimethoxy benzene give the Friedel–Crafts reaction products in very good yield. The reactions with heteroarenes show moderate yield of the product. The catalyst can be easily recycled without significant loss of activity.

Graphical abstract

α-Amido sulfones derived from various aldehydes undergo the Friedel–Crafts reactions with electron-rich arenes or heteroarenes in the presence of Amberlyst-15 as the catalyst. Amberlyst-15 can be recycled without significant loss of activity.

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Introduction

The Friedel–Crafts reactions represent a powerful tool to introduce new carbon–carbon bond in aromatic compounds.1, 1(a), 1(b) This reactions can be used for a method to build up polycyclic structure as well.2, 2(a), 2(b), 2(c) The application of α-amido sulfones has been utilized through the formation of N-acyl iminium ions on treatment with Lewis acid (Scheme 1).3, 3(a), 3(b)

The poor electrophilic properties of N-alkyl and N-aryl imines can be augmented by the substitution of electron-attracting group on nitrogen atom. The enhanced electrophilic character of N-acyliminium ions allows their reactions with a variety of nucleophiles, which have been utilized to introduce substituent at α-carbon. The reaction of N-acyl iminium ions has been utilized for the synthesis of N-arylsulfonyl α-amino nitriles,4, 4(a) N-homoallylic amines,4b α,β-dipeptides,4c (1-alkyl-1-aryl)methyl phenyl sulfones,4d and α-amino phosphonates.4e Mecozzi et al. have reported the reactions of electron-rich aromatic nucleophiles with N-acyl iminium ions catalyzed by titanium tetrachloride.4f Das et al. have utilized the α-amido sulfones for the synthesis of aza-Morita–Baylis–Hilman adduct using DABCO as an efficient catalyst.4g Ballini et al. have demonstrated that the Montmorillonite K-10 could be an efficient catalyst for the Friedel–Crafts reactions of α-amido sulfones with indoles for the synthesis of 3-substituted indoles.4h

Development of efficient and practical catalysts for the organic transformation is a considerable interest to both academia and industry.5, 5(a), 5(b) While homogeneous catalysts exhibit the advantage of high activity and selectivity in broad range of synthetic chemistry,6 their practical application remains limited due to the difficulties associated with their toxicity, disposal of acidic wastes and catalyst/product separation. Heterogeneous catalysis is an another interesting area in organic synthesis as it provides not only an alternative to homogeneous catalysis but also has the advantage of easy catalyst recovery, recycling and mild reaction condition. The introduction of solid acid catalysts such as sulfated zirconia,7, 7(a), 7(b) heteropoly acids,8 acidic polymers,9 clays and zeolites10 has enhanced the development of replacement of liquid acid catalysts for organic transformations. In this regard, acidic cation-exchange polymer resin represents a suitable solid acid material. Amberlyst-15 is one of the polymeric cation-exchange resin with sulfonic acid functionality used as heterogeneous catalysis in non-aqueous as well as aqueous media. Amberlyst-15 retains various advantages such as nontoxic, reusability, non-corrosive, chemical and physical stability and environmental compatibility. The unique properties have lead to the application of Amberlyst-15 as a powerful catalyst for various organic transformations such as Michael addition of pyrroles to α,β-unsaturated ketones.11, 11(a) This can be also utilized for the synthesis of various compounds such as benzodiazepines,11b bis and tris(1H-indole-3-yl)methanes,11c allyl amides,11d xanthenes,11(e), 11(f) α-hydroxy phosphonates,11g α-aminophosphate,11h and 2,3-unsaturated glycodides.11i

Section snippets

Results and discussions

In light of the success in developing several catalytic systems for carbon–carbon bond formation reactions,12, 12(a), 12(b), 12(c), 12(d), 12(e), 12(f), 12(g), 12(h), 12(i) we extend our studies to the Amberlyst-15-catalyzed Friedel–Crafts reactions of α-amido sulfones with electron-rich aromatic compounds and heteroarenes. This could be the first example of Amberlyst-15-catalyzed synthesis of diaryl sulfones.

Various heterogeneous catalysts have been tested for reactions of N

Summary

A novel and efficient catalytic method has been developed for the synthesis of diaryl sulfones through Friedel–Crafts reactions of α-amido sulfones with the activated arenes and heteroarenes. α-Amido sulfones derived from various types of aldehydes are coupled with activated benzenes using Amberlyst-15 as a heterogeneous catalyst. Amberlyst-15 is inexpensive, non-corrosive solid acid and can be recycled.

General

In all cases the 1H NMR (400 MHz) spectra were recorded with Varian Gemini 2000 spectrometer. Chemical shifts were reported in ppm in CDCl3 with tetramethylsilane as an internal standard. 13C NMR data were collected on a Varian Gemini 2000 spectrometer (50 MHz). All products were identified by HRMS (EI) with Jeol DMX 303.

General procedure for the synthesis of diaryl sulfones

To a mixture of α-amido sulfones (1 mmol) and 1,2,4-trimethoxy benzene or heteroarenes (1.0 mmol), Amberlyst-15 (50 mg) were added in CH2Cl2 and the mixture was stirred at reflux

Acknowledgements

The authors thank The Center for Biological Modulators of the KRICT for the financial support. Thanks are also due to BK 21 administrated by Korea Research Council.

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