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Synlett 2004(10): 1719-1722  
DOI: 10.1055/s-2004-829574
LETTER
© Georg Thieme Verlag Stuttgart · New York

Opening of N-Tosyl Aziridines with Nucleophiles Catalyzed by Phosphomolybdic Acid Supported on Silica Gel

G. D. Kishore Kumar, Sundarababu Baskaran*
Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India
Fax: +91(44)22570545; e-Mail: sbhaskar@iitm.ac.in;
Further Information

Publication History

Received 18 March 2004
Publication Date:
15 July 2004 (online)

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Abstract

An environmentally benign H3PMo12O40-SiO2-catalyzed regioselective opening of activated aziridines with alcohols, azide, cyanide and bromide, at ambient temperature to afford the corresponding β-amino derivatives in good yields is described.

Key words

phosphomolybdic acid - silica gel - aziridines - regioselectivity - alcoholysis - β-amino ether - β-azido amine - β-cyano amine - β-bromo amine

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  • Experimental Procedure.
  • 15a

    Preparation of PMA-SiO 2 Catalyst (10% by wt): To a solution of H3PMo12O40 (0.1 equiv) in MeOH, silica gel (0.9 equiv) (100-200 mesh) was added slowly and stirred at r.t. for about 6 h and MeOH was removed under reduced pressure, which yielded PMA-SiO2 as a yellow solid.

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  • 15b Preparation of β-Amino Ethers: A mixture of N-tosyl aziridine (1 mmol), alcohol (see Table 1) and PMA-SiO2 (0.01 mmol, based on PMA) in MeCN (3 mL) was stirred at r.t. for appropriate time (see Table 1). After completion of the reaction, as indicated by TLC, the solvent was removed under reduced pressure and the residue was dissolved in THF and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography on silica gel (100-200 mesh) to afford pure β-amino ethers
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  • 15c

    Preparation of β-Azido-, Cyano- and Bromo Amines: A mixture of N-tosyl aziridine (1 mmol), NaN3, NaCN or KBr (1.1 mmol) and PMA-SiO2 (0.01 mmol, based on PMA) in MeCN and H2O (3 mL, 9: 1) was stirred at r.t. for an appropriate time (see Table [2] ). After completion of the reaction, as indicated by TLC, the reaction mixture was filtered and the filtrate was concentrated and purified by column chromatography on silica gel (100-200 mesh) to afford pure β-azido-, cyano- or bromo amines.
    Spectral Data for Selected Products: Table 1, Entry 9: IR (neat): 3472, 3287, 2930, 1600, 1403, 1323, 1155, 1086 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.74 (d, J = 8.1 Hz, 2 H), 7.73-7.18 (m, 7 H), 5.53 (d, J = 8.4 Hz, 1 H, NH), 4.35 (d, J = 3.5 Hz, 1 H), 3.74 (dd, J = 11.6 and 3.1 Hz, 1 H), 3.37-3.34 (m, 1 H), 3.27-3.19 (m, 4 H), 2.43-2.40 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 143.5, 137.6, 137.3, 129.7, 128.7, 128.1, 127.0, 126.4, 86.1, 60.5, 58.8, 58.0, 21.5. MS (EI, 70 eV): m/z = 335 (1.5) [M+ + 1], 304 (1.2), 155 (20), 121 (100), 91 (60).
    Table 1, Entry 10: IR (neat): 3396, 2976, 1734, 1600, 1440, 1366, 1321, 1244, 1152, 1091, 1033, 953, 880, 812, 659 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.67 (d, J = 8.0 Hz, 2 H), 7.21 (d, J = 7.4 Hz, 2 H), 4.69-4.60 (m, 2 H), 3.17-3.12 (m, 1 H), 2.99 (s, 3 H), 2.34 (s, 3 H), 1.91 (s, 3 H), 1.61-1.18 (m, 5 H), 1.02-0.94 (m, 9 H). 13C NMR (100 MHz, CDCl3): δ = 170.7, 142.8, 139.2, 129.4, 126.9, 71.1, 62.1, 49.1, 32.9, 26.6, 22.2, 21.9, 21.4, 21.3, 20.0, 19.8. MS (EI, 70 eV): m/z = 298 (0.5) [M+ - C4H9O], 216 (10), 155 (15), 73 (100). Table 2, Entry 8: IR (KBr): 3488, 3136, 2096, 1603, 1446, 1328, 1283, 1260, 1155, 1078, 1040, 956, 806, 755, 694 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.59 (d, J = 8.2 Hz, 2 H), 7.27-7.14 (m, 7 H), 5.55 (d, J = 8.0 Hz, 1 H, NH), 4.75 (d, J = 6.2 Hz, 1 H), 3.77-3.74 (m, 1 H), 3.54-3.42 (m, 2 H), 2.61 (br s, OH), 2.40 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 143.6, 136.9, 135.8, 129.7, 128.9, 128.5, 127.1, 126.9, 66.5, 60.6, 58.6, 21.5. MS (EI, 70 eV): m/z = 347 (6) [M+ + 1], 301 (100), 274 (45), 145 (98).

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