Synlett 2013; 24(13): 1725-1727
DOI: 10.1055/s-0033-1339178
letter
© Georg Thieme Verlag Stuttgart · New York

Diastereoselective Synthesis of N-tert-Butanesulfinylamines through Addition of p-Nitrobenzyl Chloride to N-tert-Butanesulfinimines Using a TDAE ­Strategy

Cédric Spitz
Aix-Marseille Université, Institut de Chimie Radicalaire ICR, UMR CNRS 7273, Laboratoire de Pharmaco-Chimie Radicalaire, Faculté de Pharmacie, 27 Boulevard Jean Moulin – CS 30064, 13385 Marseille Cedex 05, France   Fax: +33(4)91794677   Email: patrice.vanelle@univ-amu.fr
,
Omar Khoumeri
Aix-Marseille Université, Institut de Chimie Radicalaire ICR, UMR CNRS 7273, Laboratoire de Pharmaco-Chimie Radicalaire, Faculté de Pharmacie, 27 Boulevard Jean Moulin – CS 30064, 13385 Marseille Cedex 05, France   Fax: +33(4)91794677   Email: patrice.vanelle@univ-amu.fr
,
Thierry Terme
Aix-Marseille Université, Institut de Chimie Radicalaire ICR, UMR CNRS 7273, Laboratoire de Pharmaco-Chimie Radicalaire, Faculté de Pharmacie, 27 Boulevard Jean Moulin – CS 30064, 13385 Marseille Cedex 05, France   Fax: +33(4)91794677   Email: patrice.vanelle@univ-amu.fr
,
Patrice Vanelle*
Aix-Marseille Université, Institut de Chimie Radicalaire ICR, UMR CNRS 7273, Laboratoire de Pharmaco-Chimie Radicalaire, Faculté de Pharmacie, 27 Boulevard Jean Moulin – CS 30064, 13385 Marseille Cedex 05, France   Fax: +33(4)91794677   Email: patrice.vanelle@univ-amu.fr
› Author Affiliations
Further Information

Publication History

Received: 28 March 2013

Accepted after revision: 10 May 2013

Publication Date:
20 June 2013 (online)


Abstract

An easy and efficient method of diastereoselective synthesis of N-tert-butanesulfinylamines using a TDAE strategy was developed. Good yields and diastereoselectivities were achieved using readily available N-tert-butanesulfinimines and commercially available p-nitrobenzyl chloride.

Supporting Information

 
  • References and Notes

  • 1 Hili R, Yudin AK. Nat. Chem. Biol. 2006; 2: 284
  • 2 Robak MT, Herbage MA, Ellman JA. Chem. Rev. 2010; 110: 3600
  • 3 Buesking AW, Baguley TD, Ellman JA. Org. Lett. 2011; 13: 964
    • 4a Takechi N, Aït-Mohand S, Médebielle M, Dolbier WR. Jr. Tetrahedron Lett. 2002; 43: 4317
    • 4b Pooput C, Médebielle M, Dolbier WR. Jr. Org. Lett. 2004; 6: 301
    • 4c Pooput C, Médebielle M, Dolbier WR. Jr. J. Org. Chem. 2006; 71: 3564
    • 5a Montana M, Terme T, Vanelle P. Tetrahedron Lett. 2006; 47: 6573
    • 5b Montana M, Crozet MD, Castera-Ducros C, Terme T, Vanelle P. Heterocycles 2008; 75: 925
    • 5c Since M, Terme T, Vanelle P. Tetrahedron 2009; 65: 6128
    • 5d Juspin T, Terme T, Vanelle P. Synlett 2009; 1485
    • 5e Nadji-Boukrouche AR, Khoumeri O, Terme T, Liacha M, Vanelle P. ARKIVOC 2010; (x): 358
    • 5f Montana M, Terme T, Vanelle P. Lett. Org. Chem. 2010; 7: 453
    • 5g Juspin T, Giuglio-Tonolo G, Terme T, Vanelle P. Synthesis 2010; 844
    • 6a Giuglio-Tonolo G, Terme T, Médebielle M, Vanelle P. Tetrahedron Lett. 2003; 44: 6433
    • 6b Giuglio-Tonolo G, Terme T, Médebielle M, Vanelle P. Tetrahedron Lett. 2004; 45: 5121
    • 6c Khoumeri O, Terme T, Vanelle P. Synthesis 2009; 3677
    • 6d Khoumeri O, Giuglio-Tonolo G, Crozet MD, Terme TM, Vanelle P. Tetrahedron 2011; 67: 6173
    • 6e Khoumeri O, Terme T, Vanelle P. Tetrahedron Lett. 2012; 53: 2410
  • 7 Sapountzis I, Dube H, Lewis R, Gommermann N, Knochel P. J. Org. Chem. 2005; 70: 2445
    • 8a Vanelle P, De Meo MP, Maldonado J, Nouguier R, Crozet MP, Laget M, Dumenil G. Eur. J. Med. Chem. 1990; 241
    • 8b El-Kashef HS, El-Emary TI, Gasquet M, Timon-David P, Maldonado J, Vanelle P. Pharmazie 2000; 55: 572
    • 8c Boufatah N, Gellis A, Maldonado J, Vanelle P. Tetrahedron 2004; 60: 9131
    • 8d Gellis A, Kovacic H, Boufatah N, Vanelle P. Eur. J. Med. Chem. 2008; 858
  • 9 General Procedure To a stirred solution of N-sulfinimine 2 (0.24 mmol) in DMF (1 mL) at –20 °C was added TDAE (0.2 mmol) followed by dropwise addition of a solution of p-nitrobenzyl chloride (1) in DMF (1 mL). The solution was vigorously stirred at –20 °C for 1 h and then maintained at r.t. for 2 h. H2O (5 mL) was added, and the aqueous solution was extracted with CH2Cl2 (3 × 15 mL). The combined organic layer was washed with H2O (20 mL) and dried over MgSO4. Filtration and evaporation of the solvent furnished the crude product. Purification by silica gel chromatography (EtOAc–PE: from 6:4 to 8:2 depending on the polarity of substrates) allowed pure amine products 3 as a mixture of diastereoisomers. N-[1,2-Bis(4-nitrophenyl)ethyl]-2-methylpropane-2-sulfinamide (3b) Major Diastereoisomer (R,R) Yellow solid; mp 171–174 °C. 1H NMR (200 MHz, CDCl3): δ = 8.16 (d, J = 8.6 Hz, 2 H), 8.08 (d, J = 8.5 Hz, 2 H), 7.40 (d, J = 8.6 Hz, 2 H), 7.18 (d, J = 8.5 Hz, 2 H), 4.80–4.70 (m, 1 H), 3.67 (d, J = 4.7 Hz, 1 H), 3.48 (dd, J = 13.5, 6.2 Hz, 1 H), 3.13 (dd, J = 13.5, 7.7 Hz, 1 H), 1.17 (s, 9 H). 13C NMR (50 MHz, CDCl3): δ = 48.2, 147.8, 147.1, 144.3, 130.5, 128.3, 124.2, 123.8, 60.1, 56.6, 43.0, 22.6. ESI-HRMS: m/z [M + Na]+ calcd for [C18H21N3O5SNa]+: 414.10941; found: 414.10979. Minor Diastereoisomer (R,S) Yellow solid; mp 145–148 °C. 1H NMR (200 MHz, CDCl3): δ = 8.18 (d, J = 8.8 Hz, 2 H), 8.12 (d, J = 8.7 Hz, 2 H), 7.39 (d, J = 8.8 Hz, 2 H), 7.19 (d, J = 8.7 Hz, 2 H), 4.86–4.79 (m, 1 H), 3.58 (br s, 1 H), 3.24 (dd, J = 7.3, 3.6 Hz, 2 H), 1.19 (s, 9 H). 13C NMR (50 MHz, CDCl3): δ = 148.0, 147.7, 147.4, 143.3, 130.5, 128.7, 124.11, 124.08, 59.0, 56.3, 44.7, 22.6. ESI-HRMS: m/z [M + Na]+ calcd for [C18H21N3O5SNa]+: 414.10941; found: 414.10982.
  • 10 CCDC 929478 contains the supplementary crystallographic data of compound (R,R)-3b for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif.
  • 11 Cogan DA, Ellman JA. J. Am. Chem. Soc. 1999; 121: 268
  • 12 Deprotection of Amine (R,R)-3b To a stirred solution of N-protected amine (R,R)-3b (47 mg, 0.12 mmol) in MeOH (4 mL) was added 4 M HCl in dioxane (180 μL, 0.72 mmol), and the solution was stirred at r.t. for 2 h. The reaction mixture was then concentrated under reduced pressure, diluted with EtOAc (20 mL), and washed with sat. aq NaHCO3 (20 mL). The aqueous layer was extracted twice more with EtOAc (2 × 20 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure Solvents were evaporated under vacuum. Purification by silica gel chromatography (CH2Cl2–MeOH = 95:5) allowed pure primary amine 4b (26 mg, 75%). (R)-1,2-Bis(4-nitrophenyl)ethylamine (R)-(4b) Yellow solid; mp 141–144 °C. 1H NMR (200 MHz, CD3OD): δ = 8.20 (d, J = 8.7 Hz, 2 H), 8.11 (d, J = 8.7 Hz, 2 H), 7.56 (d, J = 8.7 Hz, 2 H), 7.35 (d, J = 8.7 Hz, 2 H), 4.55–4.45 (m, 1 H), 3.27–3.14 (m, 2 H). 13C NMR (50 MHz, CD3OD): δ = 149.0, 148.4, 146.2, 146.2, 131.7, 129.3, 124.8, 124.6, 57.7, 44.4. ESI-HRMS: m/z [M + Na]+ calcd for [C14H13N3O4Na]+: 310.07983; found: 310.07965.