Synlett 2017; 28(08): 939-943
DOI: 10.1055/s-0036-1588670
letter
© Georg Thieme Verlag Stuttgart · New York

Regioselective Ring Opening of N-H-Aziridines with Sulfur Nucleophiles in Liquid SO2

Jevgeņija Lugiņina
Institute of Technology of Organic Chemistry, Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena Str. 3, Riga 1048, Latvia   Email: Maris.Turks@rtu.lv
,
Māris Turks*
Institute of Technology of Organic Chemistry, Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena Str. 3, Riga 1048, Latvia   Email: Maris.Turks@rtu.lv
› Author Affiliations
Further Information

Publication History

Received: 09 September 2016

Accepted after revision: 15 November 2016

Publication Date:
08 December 2016 (online)


Abstract

N-H-Aziridines undergo efficient ring-opening reactions with aromatic and aliphatic thiols in liquid sulfur dioxide as reaction medium. Due to the Lewis acidic nature of SO2, these reactions do not require any other catalytic additives. The expected β-alkyl/arylthio-amines (β-amino thioethers) are obtained with excellent β-regioselectivity. The developed reaction conditions are compatible with chiral starting materials the enantiomeric purity of which is conserved in the corresponding products. This method is also useful for direct synthesis of carbohydrate–amino acid conjugates and 2-iminothiazolidine derivatives.

Supporting Information

 
  • References and Notes

  • 1 Tanner D, He HM. Tetrahedron 1992; 48: 6079
  • 2 Hudlicky T, Luna H, Price JD, Rulin F. J. Org. Chem. 1990; 55: 4683
  • 3 McCoull W, Davis FA. Synthesis 2000; 1347
  • 4 Aziridines and Epoxides in Organic Synthesis. Yudin AK. Wiley-VCH; Weinheim: 2006
    • 5a Hu XE. Tetrahedron Lett. 2002; 43: 5315
    • 5b Perlman ME, Bardos TJ. J. Org. Chem. 1988; 53: 1761
  • 6 Li D, Wang Y, Wang J, Wang P, Wang K, Lin L, Liu D, Jiang X, Yang D. Chem. Commun. 2016; 52: 9640
    • 7a Bhattacharyya A, Kavitha CV, Ghorai M. J. Org. Chem. 2016; 81: 6433
    • 7b Hsueh N, Clarkson GJ, Shipman M. Org. Lett. 2015; 17: 3632
    • 7c Nonn M, Kiss L, Forrό E, Sillanpää R, Fülöp F. Tetrahedron 2014; 70: 8511
    • 7d Chawla R, Singh AK, Yadav LD. S. Tetrahedron 2013; 69: 1720
    • 8a Tanner D. Angew. Chem., Int. Ed. Engl. 1994; 33: 599
    • 8b Atkinson RS. Tetrahedron 1999; 55: 1519
    • 8c Sweeney JB. Chem. Soc. Rev. 2002; 31: 247
    • 8d Padwa A, Murphree SS. ARKIVOC 2006; (iii): 6
    • 8e Lu P. Tetrahedron 2010; 66: 2549
    • 8f Ohno H. Chem. Rev. 2014; 114: 7784
    • 8g Hu XE. Tetrahedron 2004; 60: 2701
    • 8h Callebaut G, Meiresonne T, De Kimpe N, Mangelinckx S. Chem. Rev. 2014; 114: 7954
    • 8i Ohno H. Chem. Rev. 2014; 114: 7784
  • 9 Greene’s Protective Groups in Organic Synthesis . Wuts PG. M, Greene TW. Wiley; Hoboken: 2007. 4th ed. 16-366
  • 10 Stanković S, D’hooge M, Catak S, Eum H, Waroquier M, Van Speybroeck V, De Kimpe N, Ha H.-J. Chem. Soc. Rev. 2012; 41: 643
    • 11a Wu J, Hou X.-L, Dai L.-X. J. Org. Chem. 2000; 65: 1344
    • 11b Bisol TB, Bortoluzzi AJ, Sá MM. J. Org. Chem. 2011; 76: 948
    • 11c Jat JL, Paudyal MP, Gao H, Xu Q.-L, Yousufuddin M, Devarajan D, Ess DH, Kürti L, Falck JR. Science 2014; 343: 61
  • 12 Lugiņina J, Turks M. Chem. Heterocycl. Comp. 2016; 52: 773
  • 13 Paulse H, Patt H. Liebigs Ann. Chem. 1981; 1633
  • 14 Bassindale AR, Kyle PA, Soobramaniem M.-C, Taylor PG. J. Chem. Soc., Perkin Trans. 1 2000; 439
  • 15 Wade TN. J. Org. Chem. 1980; 45: 5328
    • 16a Caiazzo A, Dalili S, Yudin AK. Org. Lett. 2002; 4: 2597
    • 16b Braga AL, Schwab RS, Alberto EE, Salmon SM, Vargas J, Azerado JB. Tetrahedron Lett. 2009; 50: 2309
    • 16c Salman SM, Schwab RS, Alberto EE, Vargas J, Dornelles L, Rodrigues OE. D, Braga AL. Synlett 2011; 69
  • 17 Lugiņina J, Uzuleņa J, Posevins D, Turks M. Eur. J. Org. Chem. 2016; 1760
  • 18 Posevins D, Suta K, Turks M. Eur. J. Org. Chem. 2016; 1414
    • 19a Deeming AS, Emmett EJ, Richards-Taylor CS, Willis MC. Synthesis 2014; 46: 2701
    • 19b Emmett EJ, Willis MC. Asian J. Org. Chem. 2015; 4: 602
    • 19c Liu G, Fan C, Wu J. Org. Biomol. Chem. 2015; 13: 1592
    • 19d Vogel P, Turks M, Bouchez L, Craita C, Huang X, Murcia MC, Fronquerne F, Didier C, Flowers C. Pure Appl. Chem. 2008; 80: 791
    • 19e Lugiņina J. Synlett 2014; 25: 2962
    • 19f Stikute A, Peipiņš V, Turks M. Tetrahedron Lett. 2015; 56: 4578
    • 19g Marković D, Tchawou WA, Novosjolova I, Laclef S, Stepanovs D, Turks M, Vogel P. Chem. Eur. J. 2016; 22: 4196
    • 19h Turks M, Lawrence AK, Vogel P. Tetrahedron Lett. 2006; 47: 2783
  • 20 Assem N, Natarajan A, Yudin AK. J. Am. Chem. Soc. 2010; 132: 10986
  • 21 Petra DG. I, Kamer PC. J, Spek AL, Schoemaker HE, van Leeuwen PW. N. M. J. Org. Chem. 2000; 65: 3010
  • 22 Wu J, Hou X.-L, Dai L.-X. J. Chem. Soc., Perkin Trans. 1 2001; 1314
  • 23 Xiong C, Wang W, Cai C, Hruby VJ. J. Org. Chem. 2002; 67: 1399
  • 24 Turks M, Rijkure I, Belyakov S, Zicane D, Kumpiņš V, Bizdena E, Meikas A, Valkna A. Chem. Heterocycl. Compd. 2012; 48: 861
  • 25 Aleksis R, Jaudzems K, Ivanova J, Žalubovskis R, Kalvinsh I, Liepinsh E. Chem. Heterocycl. Compd. 2014; 49: 1589
    • 26a Fernandez T, Sordo JA, Monnat F, Deguin B, Vogel P. J. Am. Chem. Soc. 1998; 120: 13276
    • 26b Monnat F, Vogel P, Rayon VM, Sordo JA. J. Org. Chem. 2002; 67: 1882
    • 26c Vogel P, Sordo JA. Curr. Org. Chem. 2006; 10: 2007
    • 26d Mingos DM. P. Struct. Bonding (Berlin, Ger.) 2014; 154: 1
    • 26e Li J, Rogachev AY. Phys. Chem. Chem. Phys. 2015; 17: 1987
    • 26f Vogel P, Turks M, Bouchez L, Markovic D, Varela-Alvarez A, Sordo JA. Acc. Chem. Res. 2007; 40: 931
  • 27 General Procedure for Aziridine Ring Opening at –10 °C (S)-Aziridine-2-carboxamide (1; 0.10 g, 1.17 mmol, 1 equiv) and 4-chlorobenzenethiol (2a; 0.34 g, 2.35 mmol, 2 equiv), were placed into a two-neck round-bottom flask equipped with dry ice condenser under inert atmosphere. Sulfur dioxide (35 ± 5 mL) was condensed into the flask at –78 °C. The resulting reaction mixture was allowed to warm up to the boiling point of SO2 (–10 °C), and the reaction was performed in liquid SO2 under the same temperature for 5 h. Then the flask was connected to SO2-collecting vessel cooled at –78 °C, and the excess of SO2 was transferred. The solid residue was purified by column chromatography (4% EtOH–CH2Cl2) and (R)-2-amino-3-[(4-chlorophenyl)thio]propanamide (3a, 149 mg, 55%) was obtained as an amorphous powder; [α]D 25 –53.5 (c 1.0, CHCl3). IR (KBr): 3380, 3330, 3075, 3185, 1655, 1635, 1575, 1540, 1505, 1495, 1475, 1425, 1390, 1095, 1010, 815, 810, 730, 705, 675 cm–1. 1H NMR (300 MHz, DMSO-d 6): δ = 7.41 (br s, 1 H, CONH), 7.40–7.31 [m, 4 H, H-C(Ar)], 7.10 (br s, 1 H, CONH), 3.33–3.19 [m, 2 H, Ha-C(3), H-C(2)], 2.98 [dd, 1 H, 2 J = 12.4 Hz, 3 J = 7.0 Hz, Hb-C(3)], 1.99 [br s, 1 H, H2N-C(2)]. 13C NMR (75.5 MHz, DMSO-d 6): δ = 175.1, 135.6, 130.1, 129.7, 128.8, 54.0, 38.4. HRMS: m/z calcd [C9H11ClN2OS + H+]: 231.0354; found: 231.0355.
    • 28a Kreituss I, Rozenberga E, Zemitis J, Trapencieris P, Romanchikova N, Turks M. Chem. Heterocycl. Compd. 2013; 49: 1108
    • 28b Romanchikova N, Trapencieris P, Zemitis J, Turks M. J. Med. Chem. Enz. Inhib. 2014; 29: 765
  • 29 General Procedure for Aziridine Ring Opening at 25 °C 1-(Aziridin-2-ylmethyl)-4-[4-(trifluoromethyl)phenyl]-1H-1,2,3-triazole (6; 0.05 g, 0.19 mmol, 1 equiv) and dodecane-1-thiol (2b; 89 μL, 0.37 mmol, 2 equiv) were placed into a stainless steel vessel. Three vacuum/nitrogen cycles were accomplished via Schlenk line. Sulfur dioxide (25 ± 2 g) was transferred into the vessel at –78 °C. Reaction was carried out under pressure (4 bar) at 25 °C for 14 h. Then the SO2-collecting vessel was cooled to –78 °C, connected to the reaction vessel, and the excess of SO2 was transferred. The resulting residue was purified by column chromatography (3% EtOH–CH2Cl2), and compound 9b (83 mg, 95%) was obtained as an amorphous powder. IR (KBr): 3385, 3315, 3135, 3115, 2965, 2920, 2850, 1620, 1470, 1335, 1230, 1190, 1170, 1125, 1065, 845, 825, 720, 695, 600 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.99 [s, 1 H, H-C(triaz)], 7.95 [d, 3 J = 8.2 Hz, 2 H, H-C(Ar)], 7.67 [d, 3 J = 8.2 Hz, 2 H, H-C(Ar)], 4.56 (dd, 2 J = 13.7 Hz, 3 J = 4.2 Hz, 1 H, Ha-C(3)], 4.34 [dd, 2 J = 13.7 Hz, 3 J = 7.3 Hz, 1 H, Hb-C(3)], 3.53–3.40 [m, 1 H, H-C(2)], 2.67 [dd, 2 J = 13.4 Hz, 3 J = 5.4 Hz, 1 H, Ha-C(1)], 2.58–2.44 [m, 3 H, Hb-C(1), CH2-S], 1.66–1.49 (m, 4 H, CH2, NH2), 1.44–1.14 (m, 18 H, 9 CH2), 0.87 (t, 3 J = 6.6 Hz, 3 H, Me). 13C NMR (75 MHz, CDCl3): δ = 146.2, 134.0, 130.0 (q, 2 J C–F = 32 Hz), 125.8 (q, 3 J C–F = 4 Hz), 125.8, 124.5 (q, 1 J C–F = 272 Hz), 121.6, 55.7, 50.9, 37.5, 32.7, 31.9, 29.6, 29.6, 29.6, 29.5, 29.5, 29.3, 29.2, 28.8, 22.6, 14.1. HRMS: m/z calcd [C24H37F3N4S + H+]: 471.2759; found: 471.2780.
  • 30 CCDC 1479668 (for compound 11) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.