Reaction of α-Halo-Enones with Heterocyclic Bases. A Mild and Efficient Synthesis of Amino-Steroids

References

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• Kuehne , M. E. and Nelson , J. A. 1970 . J. Org. Chem. , 35 : 161 by the ring opening with HBr-HOAc (r.t., 100hr) in 67% yield: colorless prisms, m.p. 47–48°; IR ν max.1680, 1570 cm −1; UV Λ max. 259 nm(∊ 11200); 1H-NMR δ (CDCl3); 3.19 (1H, br.d, J=14.5Hz, WH=8.0HZ), 1.28 (3H, s).Prepared from 1,9-epoxy-10-methyloctal-2-one
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• IR spectra were determined for Nujol mulls with a Jasco A-102 spectrophotometer unless stated otherwise and 1H-NMR spectra were measured in CDCl3 solutions with a JEOL FX-90Q spectrometer and chemical shifts are given in ppm downfield from internal TMS. Satisfactory mass spectra and elemental analyses were obtained for all compounds. Selected IR and NMR data as follows:
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• ν 3450, 1670, 1595 cm −1; δ 3.38 (1H, br. d, J[dbnd]14.5Hz), 2.92 (4H, m), 2.54 (4H, m), 1.17 (3H, s). Ia′: ν 3480, 1670, 1615 cm −1; δ 5.75 (1H, s), 2.45 (8H, m), 1.35 (3H, s). Ib: ν 1675, 1585 cm −1; δ 3.48 (1H, br. d, J[dbnd]14.5Hz), 2.98 (4H, t, J[dbnd]5.0Hz), 2.43 (4H, t, J[dbnd]5.0Hz), 1.17 (3H, s). Ib′: ν 1675, 1610 cm −1; δ 5.75 (1H, s), 2.40 (8H, s), 1.36 (3H, s). Ic-acetate: ν 1670, 1645, 1585 cm −1; δ 3.42 (1H, m), 3.42 (4H, m), 2.90 (4H, m), 1.18 (3H, s). Ic′-acetate: ν 1680, 1650, 1610 cm −1; δ 5.71 (1H, s), 3.50 (4H, m), 2.38 (4H, m), 1.38 (3H, s). Id: ν 1680, 1595 cm −1; δ 3.65 (4H, t, J[dbnd]5.0Hz), 3.42 (1H, br. d, J[dbnd]14.5Hz), 2.89 (4H, t, J[dbnd]5.0Hz), 1.16 (3H, s). Id′: ν 1675, 1615 cm −1; δ 5.72 (1H, s), 3.63 (4H, t, J[dbnd]4.5Hz), 2.35 (4H, t, J[dbnd]4.5Hz), 1.38 (3H, s).
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• ν 3340, 1724, 1660, 1575 cm −1; δ 3.42 (1H, br. d, J[dbnd]14.5Hz), 3.00 (4H, m), 2.68 (4H, m), 1.17 (3H, s). IIa′: ν 3340, 1725, 1675, 1610 cm −1; δ 5.78 (1H, s), 2.53 (8H, m), 1.37 (3H, s). IIb: ν 1720, 1668, 1585 cm −1; δ 3.40 (1H, br. d, J[dbnd]14.5Hz), 3.07 (4H, m), 2.74 (4H, m), 1.18 (3H, s). IIb′: ν 1730, 1680, 1608 cm −1; δ 5.79 (1H, s), 2.49 (8H, s), 1.37 (3H, s). IIc-acetate: ν 1737, 1678, 1647, 1585 cm −1; δ 3.43 (1H, m), 3.43 (4H, m), 2.90 (4H, m), 1.23 (3H, s). IIc′-acetate: ν 1738, 1680, 1658, 1610 cm −1; δ 5.73 (1H, s), 3.50 (4H, m), 2.38 (4H, m), 1.38 (3H, s). IId: ν 1735, 1672, 1580 cm −1; δ 3.70 (4H, t, J[dbnd]4.5 Hz), 3.34 (1H, br. d, J[dbnd]14.5Hz), 2.94 (4H, t, J[dbnd]4.5 Hz), 1.18 (3H, s). IId′: ν 1736, 1678, 1608 cm −1; δ 5.72 (1H, s), 3.65 (4H, t, J[dbnd]4.5Hz), 2.35 (4H, t, J[dbnd]4.5Hz), 1.36 (3H, s).
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• ν 3400, 1660, 1585 cm −1; δ 3.35 (1H, br. d, J[dbnd]14.5Hz), 2.97 (4H, t, J[dbnd]5.5Hz), 2.62 (4H, m), 1.20 (3H, s). IIIa′: ν (film) 3400, 1660, 1610 cm −1; δ 5.73 (1H, s), 2.57 (8H, m), 1.42 (3H, s). IIIb: ν 1660, 1585 cm −1; δ 3.36 (1H, br. d, J[dbnd]14.5Hz), 2.97 (4H, t, J[dbnd]4.4Hz), 2.43 (4H, t, J[dbnd]4.4Hz), 1.18 (3H, s). IIIb′: ν 1670, 1605 cm −1; δ 5.73 (1H, s), 2.41 (8H, s), 1.43 (3H, s). IIIc-acetate: ν (film) 1680, 1660, 1585 cm −1; δ 3.45 (4H, m), 3.42 (1H, m), 2.90 (4H, m), 1.21 (3H, s). IIIc′-acetate: δ (film) 1675, 1650, 1610 cm −1; δ 5.71 (1H, s), 3.50 (4H, m), 2.34 (4H, m), 1.43 (3H, s). IIId: ν 1665, 1590 cm −1; δ 3.68 (4H, t, J[dbnd]5.0Hz), 3.33 (1H, br. d, J[dbnd]14.5Hz), 2.90 (4H, t, J[dbnd]5.0Hz, 1.22 (3H, s). IIId′: ν 1675, 1610 cm −1; δ 5.76 (1H, s), 3.67 (4H, t, J[dbnd]4.8Hz), 2.38 (4H, t, J[dbnd]4.8Hz), 1.45 (3H, s).
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• Tomoeda , M. , Inuzuka , M. , Furuta , T. and Takahashi , T. 1964 . Tetrahedron Letters , : 1233 The unusually large downfield shift of the doublet is presumably due to the deshielding effect of the α-amino function and the similar effect was reported in 4-substituted cholest-4-en-3-one analogs. See
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