Novel Radical Cyclization of N-Aziridinyl Imines

Journal of the American Chemical Society

Volumn 113, Issue 26, 1991, Pages 9882-9883

  Kim, Sunggak ^a   Kee, In Seo ^a   Lee, Sangphil ^a  

^a Korea Advanced Institute of Science and Technology (KAIST)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 84918748913     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00026a041     Document Type: Article

References (42)

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32. CAUTION! After preparation of l-amino-2-phenylaziridinium acetate (approximately 10-g scale) by the known procedure (Muller, R. K.; Joos, R.; Felix, D.; Schreiber, J.; Wintner, C.; Eschenmoser, A. Org. Synth. 1976, 55, 114), it exploded during storage at room temperature, causing minor injuries. The cause of the explosion is unclear at present. Thus, it is desirable to use a pentane solution of l-amino-2-phenylaziridine for the preparation of N-aziridinyl imines.
33. The byproduct was 1-(2′-phenylaziridinyl)-4,4-bis(ethoxycarbonyl)-piperidine. Furthermore, it was obtained in 75% yield without the formation of 2a when la was treated with n-Bu3SnH in refluxing benzene for 4 h without the addition of AIBN. 1H NMR (300 MHz, CDC13, −50 °C): δ 1.19 (t, 3 H, J = 7.1 Hz), 1.21 (t, 3 H, J = 7.1 Hz), 1.89 (t, 2 H, J = 11.5 Hz), 2.10 (d, 1H, J = 4.5 Hz), 2.15 (d, 1H, J= 7.64 Hz), 2.28–2.51 (m, 4 H), 2.72 (dd, 1H, J = 4.8, 7.9 Hz), 3.08–3.11 (m, 2 H), 4.12 (q, 2H, J= 7.1 Hz), 4.16 (q, 2 H, J = 7.1 Hz), 7.16–7.32 (m, 5 H). IR (NaCl): 2952, 1733, 1452, 1367, 1246, 1129 cm-−1. HRMS (M+): calcd for C19H26O4N2 346.1892, found 346.1877.
34. The structures of 6a and 6b were further ascertained by 1H NMR analysis of the destannylated products after treatment of 6a and 6b with DC1, respectively.
35. Satisfactory spectral data and high-resolution mass spectra were obtained for the reaction products.
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40. Additional AIBN (0.1 equiv) was added after 2 h.
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42. Treatment of 15 with n-Bu3SnH (1.1 equiv) and AIBN (0.1 equiv) in benzene (0.01 M) at 80 °C for 4 h afforded 16 in 92% yield. The ratio of cis and trans isomer (16) could not be determined by 1H NMR.