Elsevier

Tetrahedron Letters

Volume 60, Issue 23, 6 June 2019, Pages 1526-1529
Tetrahedron Letters

Metal free oxidative Cdouble bondC bond cleavage: Facile and one-pot tandem synthesis of benzothiadiazine-1,1-dioxides

https://doi.org/10.1016/j.tetlet.2019.05.002Get rights and content

Highlights

  • Simple one-pot synthesis of biologically active benzothiadiazine-1,1-dioxides.

  • Metal free protocol.

  • Chiefly accessible substrates.

  • Wide functional group tolerance.

  • Good to moderate yield of the products.

Abstract

An interesting protocol for the synthesis of benzothiadiazine-1,1-dioxides through iodine-catalyzed one-pot dehomologative oxidation of styrenes and readily available 2-aminobenzenesulfonamide has been developed. Diverse benzothiadiazine-1,1-dioxides were prepared using I2 as a catalyst, TBHP as an oxidant and Na2CO3 as a base. This reliable, metal and ligand free conversion involves dehomologation of styrene to aromatic aldehyde which on subsequent cyclisation affords benzothiadiazine-1,1-dioxides in good yield.

Introduction

Synthesis of heterocyclic compounds is one of the most adorable branch in organic synthesis, due to the significant role of heterocycles in pharmaceuticals, natural products, advanced materials, crop protecting agents [1]. Amongst them benzothidiazine-1,1-dioxides belong to the important class of fused heterocyclic scaffolds because of their diverse biological and pharmacological activities including diuretic [2], antihypertensive [3], anticancer [4], antiviral [5], anti-microbial [6] along with KATP channel activators [7] as well as α1-adrenoceptor antagonists [8].

Copious methodologies have been developed for the preparation of benzothiadiazine-1,1-dioxides by concerning their widespread applications. In last few decades, plenty of methods have been developed for the synthesis of benzothiadiazine-1,1-dioxides. Okano et al. in 1979 reported first for the synthesis of benzothiadiazine-1,1-dioxides using aryl carboxylic acids [9]. The reactions of 2-aminobenzenesulfonamide with carboxylic acid derivatives under harsh conditions are the typical synthetic procedures for the synthesis of benzothiadiazine-1,1-dioxides [10]. Afterwards, various reports were published for the synthesis of benzothiadiazine-1,1-dioxides using aldehydes [11], benzyl alcohols [12] and methylarenes [13]. Another strategy used for the synthesis of 1,2,4-benzothiadiazine-1,1-dioxide involves transition metal catalyzed reactions. An efficient method for the synthesis of benzothiadiazine-1,1-dioxides through iron-catalyzed cascade coupling of 2-bromobenzenesulfonamide with amidine hydrochlorides has been developed by Yang et al. [14]. Whereas, Su and co-workers produced via reductive cyclization of N,N diethyl 2-nitro benzenesulfonamide with nitriles using SmI2 as a reducing agent [15]. Similarly, benzothiadiazine-1,1-dioxides could also be synthesized through condensation of o-halosubstituted benzenesulfonyl chloride with amidines as reported by Cherepakha et al. [16]. K2S2O8-mediated, a transition-metal-free, intramolecular oxidative nitrogenation of C(sp3)-H in N-aryl benzylic amines followed by oxidation has been developed by Laha and co-workers in 2015 [17]. Very recently, Liu et al. have developed palladium-catalyzed oxidative cleavage tandem cyclization reaction of anilines and terminal alkenes for the concise synthesis of various quinazolinone derivatives and benzothiadiazine-1,1-dioxide (Fig. 1(a)) [18].

The transition metal-based protocols, although successful, still have some inherent limitations and environmental toxicity. Considering the advantages of iodine catalyzed oxidation reactions, we decided to continue our research work [19] and here for direct oxidative synthesis of benzothiadiazine-1,1-dioxides from styrene and 2-aminobenzenesulfonamide as a successive protocol (Fig. 1(b)) [20].

Section snippets

Results and discussion

Our previously obtained results for the synthesis of biologically active heterocycles [21], channeled our interest to explore our hypothesis for the synthesis of benzothiadiazine-1,1-dioxides. We began our study with a model reaction of styrene (1a) (1.0 equiv.) 2-aminobenzenesulfonamide (2a) (1.0 equiv.) in tert-butyl hydroperoxide (TBHP) (70% in H2O; 10 equiv.), iodine and various bases (Table 1). Initially, we started optimization of our proposed protocol using styrene (1a) (1.0 equiv.) in

Conclusions

We have demonstrated the general and efficient method for the synthesis of benzothiadiazine-1,1-dioxide via dehomologative oxidation of styrene. A variety of advisable products were obtained in good to moderate yields with high atom economy under environmentally gentle conditions. Notably, this method will facilitate metal and ligand free protocol and one pot formation of biologically salient heterocycles in iodine/TBHP mediated system.

Acknowledgments

B.N.P. and P.A.S. thanks to UGC, New Delhi, India for providing fellowship. A.S.K. and A.C.C. greatly appreciate the generous financial support from the Defence Research and Development Organization (DRDO) (ERIP/ER/1503212/M/01/1666), New Delhi, India.

References (22)

  • M. Dibella et al.

    Farmaco

    (1973)
  • D. Yang et al.

    J. Comb. Chem.

    (2009)
  • W. Su et al.

    J. Chem. Res.

    (2004)
  • W. Liu et al.

    Org. Chem. Front.

    (2018)
  • L.F. Tietze et al.

    Domino Reactions in Organic Synthesis

    (2006)
    B. Willy et al.

    Curr. Org. Chem.

    (2009)
    D.M. D’Souza et al.

    Chem. Soc. Rev.

    (2007)
    L.F. Tietze

    Chem. Rev.

    (1996)
    X.-F. Wu et al.

    Chem. Rev.

    (2013)
    F. Bellina et al.

    Tetrahedron

    (2009)
    B. Heller et al.

    Chem. Soc. Rev.

    (2007)
    J. Alvarez-Builla et al.

    Modern Heterocyclic Chemistry

    (2011)
  • F.C. Novello et al.

    J. Am. Chem. Soc.

    (1957)
    J.-H. Short et al.

    J. Am. Chem. Soc.

    (1960)
  • A.A. Rubin et al.

    Science

    (1961)
    J.G. Topliss et al.

    J. Med. Chem.

    (1964)
    J.G. Topliss et al.

    J. Med. Chem.

    (1972)
    A. Tait et al.

    Bioorg. Med. Chem. Lett.

    (2005)
  • A. Kamal et al.

    Bioorg. Med. Chem. Lett.

    (2007)
    J.-W. Chern et al.

    Heterocycles

    (1993)
    A. Scozzofava et al.

    Curr. Med. Chem.

    (2003)
    S. Khelili et al.

    Eur. J. Med. Chem.

    (2012)
  • P. Zhan et al.

    Curr. Med. Chem.

    (2008)
  • S. Boverie et al.

    J. Med. Chem.

    (2005)
    P. Tullio et al.

    J. Med. Chem.

    (2005)
    S. Lachenicht et al.

    ChemMedChem

    (2009)
  • J.-W. Chern et al.

    J. Med. Chem.

    (1998)
    A. Tait et al.

    Bioorg. Med. Chem. Lett.

    (2005)
  • Cited by (8)

    • Iodine-catalyzed tandem oxidative aromatization for the synthesis of meta-substituted alkoxybenzenes

      2021, Tetrahedron
      Citation Excerpt :

      The increasing demands of environmentally benign chemistry have promoted the chemical industries to minimize waste production in organic synthesis [1], [2]. One-pot or tandem reactions can generally provide such an approach because they avoid tedious manipulation processes and thus reduce the produce of wastes in them [3-7]. The construction of substituted alkoxybenzenes has attracted great interests among synthetic chemists because of their widely application in the preparation of high–value pharmaceuticals such as farnesyl protein transferase inhibitors [8], agrochemicals [9], oligomers [10], as well as building blocks in organic synthesis [11].

    View all citing articles on Scopus
    View full text