Advertisement

Intramolecular Arylation of 2-Nitrobenzenesulfonamides: A Route to Diverse Nitrogenous Heterocycles

  • Eva Schütznerová
  • Viktor KrchňákEmail author
Chapter
Part of the Topics in Heterocyclic Chemistry book series (TOPICS, volume 52)

Abstract

In addition to being an integral component of numerous drugs, 2- and 4-nitrobenzenesulfonyl (Nos) groups are used as protecting/activating agents for the selective alkylation of primary amines. 2-Nos amides are also useful intermediates for the synthesis of fused nitrogenous heterocycles. This chapter focuses on the use of 2-Nos amides as intramolecular arylation agents and on the application of C- and N-aryl derivatives for the synthesis of diverse heterocycles in the solid phase.

Keywords

Arylation Heterocycles Nitrobenzenesulfonamides Solid-phase synthesis 

Notes

Acknowledgement

This research was supported by the Department of Chemistry and Biochemistry, University of Notre Dame, by National program of Sustainability (LO1304), and research grant 16-06446S from the Czech Science Foundation (GACR).

References

  1. 1.
    Fukuyama T, Jow CK, Cheung M (1995) 2- and 4-nitrobenzenesulfonamides: exceptionally versatile means for preparation of secondary amines and protection of amines. Tetrahedron Lett 36(36):6373–6374CrossRefGoogle Scholar
  2. 2.
    Biron E, Kessler H (2005) Convenient synthesis of N-methylamino acids compatible with fmoc solid-phase peptide synthesis. J Org Chem 70(13):5183–5189CrossRefGoogle Scholar
  3. 3.
    Miller SC, Scanlan TS (1997) Site-selective N-methylation of peptides on solid support. J Am Chem Soc 119(9):2301–2302CrossRefGoogle Scholar
  4. 4.
    Lemrova B, Soural M (2012) Solid-Phase Synthesis of 4,7,8-Trisubstituted 1,2,3,4-Tetrahydro-benzo[e][1,4]diazepin-5-ones. ACS Comb Sci 14(12):645–650CrossRefGoogle Scholar
  5. 5.
    Fulopova V, Gucky T, Grepl M, Soural M (2012) Solid-phase synthesis of trisubstituted benzo[1,4]-diazepin-5-one derivatives. ACS Comb Sci 14(12):651–656CrossRefGoogle Scholar
  6. 6.
    Fulopova V, Soural M (2015) Mining the chemical space: application of 2/4-nitrobenzenesulfonamides in solid-phase synthesis. ACS Comb Sci 17(10):570–591CrossRefGoogle Scholar
  7. 7.
    Kleb KG (1968) New rearrangement of the smiles reaction type. Angew Chem Int Ed Engl 7(4):291CrossRefGoogle Scholar
  8. 8.
    Meng Q, Thibblin A (1997) Mechanisms of solvent- and base-promoted imine-forming elimination reactions. J Am Chem Soc 119(6):1224–1229CrossRefGoogle Scholar
  9. 9.
    Bowman WR, Coghlan DR (1997) A facile method for the N-alkylation of α-amino esters. Tetrahedron 53(46):15787–15798CrossRefGoogle Scholar
  10. 10.
    Wilson MW, Ault-Justus SE, Hodges JC, Rubin JR (1999) A facile rearrangement of N-alkyl, N-(o or p-nitrophenylsulfonamide)-α-amino esters. Tetrahedron 55(6):1647–1656CrossRefGoogle Scholar
  11. 11.
    Lupi V, Penso M, Foschi F, Gassa F, Mihali V, Tagliabue A (2009) Highly stereoselective intramolecular α-arylation of self-stabilized non-racemic enolates: synthesis of α-quaternary α-amino acid derivatives. Chem Commun (33):5012–5014Google Scholar
  12. 12.
    Bouillon I, Zajicek J, Pudelova N, Krchnak V (2008) Remarkably efficient synthesis of 2H-indazole 1-oxides and 2H-indazoles via tandem carbon-carbon followed by nitrogen-nitrogen bond formation. J Org Chem 73(22):9027–9032CrossRefGoogle Scholar
  13. 13.
    Muth CW, Abraham N, Linfield ML, Wotring RB, Pacofsky EA (1960) Condensation reactions of a nitro group. II. Phenanthridine 5-oxides and benzo[c]cinnoline 1-oxide. J Org Chem 25:736–740CrossRefGoogle Scholar
  14. 14.
    Pudelova N, Krchnak V (2009) Efficient traceless solid-phase synthesis of 3,4-dihydropyrazino[1,2-b]indazoles and their 6-oxides. J Comb Chem 11(3):370–374CrossRefGoogle Scholar
  15. 15.
    Koci J, Krchnak V (2010) Solid-phase synthesis and chemical properties of 2-(2-amino/hydroxyethyl)-1-aryl-3,4-dihydropyrazino[1,2-b]indazol-2-iums. J Comb Chem 12(1):168–175CrossRefGoogle Scholar
  16. 16.
    Koci J, Oliver AG, Krchnak V (2010) Unprecedented rearrangement of 2-(2-aminoethyl)-1-aryl-3,4-dihydropyrazino[1,2-b]indazole-2-ium 6-oxides to 2,3-dihydro-1H-imidazo[1,2-b]indazoles. J Org Chem 75(2):502–505CrossRefGoogle Scholar
  17. 17.
    Schutznerova E, Krchnak V (2016) N-oxide as an intramolecular oxidant in the baeyer-villiger oxidation: synthesis of 2-alkyl-2h-indazol-3-yl benzoates and 2-alkyl-1,2-dihydro-3H-indazol-3-ones. J Org Chem 81(9):3585–3596CrossRefGoogle Scholar
  18. 18.
    Krupkova S, Slough GA, Krchnak V (2010) Synthesis of quinazolines from N-(2-nitrophenylsulfonyl)iminodiacetate and alpha-(2-nitrophenylsulfonyl)amino ketones via 2H-indazole 1-oxides. J Org Chem 75(13):4562–4566CrossRefGoogle Scholar
  19. 19.
    Boehm HJ, Flohr A, Stahl M (2004) Scaffold hopping. Drug Discov Today Technol 1(3):217–224CrossRefGoogle Scholar
  20. 20.
    Schneider G, Neidhart W, Giller T, Schmid G (1999) “Scaffold-Hopping” by topological pharmacophore search: a contribution to virtual screening. Angew Chem Int Ed 38(19):2894–2896CrossRefGoogle Scholar
  21. 21.
    Bonanomi M, Palazzo G (1977) Products of the reaction between 1H-indazol-3-ol and ethyl chloroacetate. Farmaco Sci 32(7):490–501Google Scholar
  22. 22.
    Fulopova V, Cziesla L, Fleming M, Lu Y, Voelker A, Krchnak V (2015) Traceless solid-phase synthesis of trisubstituted quinazolines. ACS Comb Sci 17(8):470–473CrossRefGoogle Scholar
  23. 23.
    Schutznerova E, Krchnak V (2015) Solid-phase synthesis of 2-aryl-3-alkylamino-1H-indoles from 2-nitro-N-(2-oxo-2-arylethyl)benzenesulfonamides via base-mediated C-arylation. ACS Comb Sci 17(2):137–146CrossRefGoogle Scholar
  24. 24.
    Gimenez-Navarro V, Volna T, Krchnak V (2015) 3-alkyl-3-(alkylamino)indolin-2-ones via base-mediated C-arylation of 2-nitrobenzenesulfonamides. ACS Comb Sci 17(8):433–436CrossRefGoogle Scholar
  25. 25.
    Carbain B, Schuetznerova E, Pribylka A, Krchnak V (2016) Solid-phase synthesis of 3,4-dihydroquinoxalin-2(1H)-ones via the cyclative cleavage of N-arylated carboxamides. Adv Synth Catal 358(5):701–706CrossRefGoogle Scholar
  26. 26.
    Kisseljova K, Smyslova P, Krchnak V (2014) Benzhydrylamines via base-mediated intramolecular sp3 C-arylation of N-benzyl-2-nitrobenzenesulfonamides-advanced intermediates for the synthesis of nitrogenous heterocycles. ACS Comb Sci 16(10):573–577CrossRefGoogle Scholar
  27. 27.
    Smyslova P, Kisseljova K, Krchnak V (2014) Base-mediated intramolecular C- and N-arylation of N,N-disubstituted 2-nitrobenzenesulfonamides: advanced intermediates for the synthesis of diverse nitrogenous heterocycles. ACS Comb Sci 16(9):500–505CrossRefGoogle Scholar
  28. 28.
    Makino S, Nakanishi E, Tsuji T (2003) Efficient synthesis of 2,4-disubstituted 1,2,4-benzothiadiazin-3-one 1,1-dioxides on solid support. J Comb Chem 5(1):73–78CrossRefGoogle Scholar
  29. 29.
    Cankarova N, La Venia A, Krchnak V (2014) Polymer-supported stereoselective synthesis of tetrahydrobenzopyrazino-thiadiazinone dioxides via N-sulfonyl iminiums. ACS Comb Sci 16(6):293–302CrossRefGoogle Scholar
  30. 30.
    Kaplanek R, Krchnak V (2013) Fast and effective reduction of nitroarenes by sodium dithionite under PTC conditions: application in solid-phase synthesis. Tetrahedron Lett 54:2600–2603CrossRefGoogle Scholar
  31. 31.
    Fulopova V, Krchnak V (2014) Solid-phase synthesis of trisubstituted 2,5-dihydrobenzo[f][1,2,5]thiadiazepine 1,1-dioxide derivatives. ACS Comb Sci 16(8):412–420CrossRefGoogle Scholar
  32. 32.
    Fulopova V, Krchnakova A, Schutznerova E, Zajicek J, Krchnak V (2015) Ring contraction of 2,5-dihydrobenzo[f][1,2,5]thiadiazepine 1,1-dioxides: access to 4H-benzo[b][1,4]thiazine 1,1-dioxides. J Org Chem 80(3):1795–1801CrossRefGoogle Scholar
  33. 33.
    Trapani P, Volna T, Soural M (2016) Solid-phase synthesis of 2,3-dihydrobenzo[f][1,2,5]thiadiazepin-4(5H)-one 1,1-dioxides with three diversity positions. ACS Comb Sci 18(6):349–354CrossRefGoogle Scholar
  34. 34.
    McMaster C, Fulopova V, Popa I, Grepl M, Soural M (2014) Solid-phase synthesis of anagrelide sulfonyl analogues. ACS Comb Sci 16(5):221–224CrossRefGoogle Scholar
  35. 35.
    Schutznerova E, Verdia P, Krchnak V (2016) Fused ring molecular scaffold with 3D architecture for constrained peptidomimetics: polymer-supported stereoselective synthesis of tetrahydrobenzo[e]pyrazino[2,1-c][1,2,4]thiadiazinone 6,6-dioxide via N-acyl Iminiums. ACS Comb Sci 18(10):655–659CrossRefGoogle Scholar
  36. 36.
    Maryanoff BE, Zhang HC, Cohen JH, Turchi IJ, Maryanoff CA (2004) Cyclizations of N-acyliminium ions. Chem Rev 104(3):1431–1628CrossRefGoogle Scholar

Copyright information

© Springer International Publishing AG 2017

Authors and Affiliations

  1. 1.Faculty of Medicine, Institute of Molecular and Translation MedicinePalacký UniversityOlomoucCzech Republic
  2. 2.Department of Organic Chemistry, Faculty of SciencePalacký UniversityOlomoucCzech Republic
  3. 3.Department of Chemistry and BiochemistryUniversity of Notre DameNotre DameUSA

Personalised recommendations