Substituted Se-Phenyl Selenocarboxylates from Terminal Alkynes
FULL PAPER
CDCl3, 25 °C, TMS): δ ϭ 2.0 (tdd, JH,H ϭ 7.1, 6.4, 5.7 Hz, 2 H,
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1-[3-Oxo-3-(phenylseleno)propyl]undecyl Acetate (4h): Yield 66%
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(0.56 g); oil. H NMR (200 MHz, CDCl3, 25 °C, TMS): δ ϭ 0.89 CH2), 2.01 (s, 3 H, CH3), 2.03 (s, 3 H, CH3), 2.07 (s, 3 H, CH3),
3
3
(t, JH,H ϭ 6.7 Hz, 3 H, CH3), 1.18Ϫ1.38 (m, 16 H, CH2),
2.08 (s, 3 H, CH3), 2.80 (t, JH,H ϭ 7.1 Hz, 2 H, CH2), 3.58 (dt,
1.40Ϫ1.64 (m, 2 H, CH2), 1.75Ϫ2.1 (m, 2 H, CH2), 2.02 (s, 3 H, 2JH,H ϭ 9.9, JH,H ϭ 6.4 Hz, 1 H, CH2), 3.70 (ddd, JH,H ϭ 9.6,
3
3
3
3
2
3
CH3), 2.72 (t, JH,H ϭ 7.5 Hz, 2 H, CH2), 4.88 (tt, JH,H ϭ 7.4,
4.8, 2.3 Hz, 1 H, CH), 3.90 (dt, JH,H ϭ 9.9, JH,H ϭ 5.7 Hz, 1 H,
5.0 Hz, 1 H, CH), 7.30Ϫ7.40 (m, 3 H, CH), 7.46Ϫ7.55 (m, 2 H, CH2), 4.13 (dd, 2JH,H ϭ 12.3, 3JH,H ϭ 2.3 Hz, 1 H, CH2), 4.25 (dd,
CH) ppm. 13C NMR (50 MHz, CDCl3, 25 °C, TMS): δ ϭ 13.9, 2JH,H ϭ 12.3, 3JH,H ϭ 4.8 Hz, 1 H, CH2), 4.50 (d, JH,H ϭ 8.0 Hz,
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20.9, 22.5, 25.1, 29.2 (3 C), 29.3 (3 C), 31.7, 33.9, 43.3, 72.8, 126.3,
1 H, CH), 4.98 (dd, 3JH,H ϭ 9.6, 8.0 Hz, 1 H, CH), 5.18 (t, 3JH,H ϭ
9.6 Hz, 1 H, CH), 5.20 (t, JH,H ϭ 9.6 Hz, 1 H, CH), 7.35Ϫ7.44
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128.7, 129.2 (2 C), 135.6 (2 C), 170.3, 199.1 ppm. GC-MS: m/z
(%) ϭ 269 (6) [M Ϫ 157]ϩ, 227 (100), 191 (11), 157 (12), 97 (16), (m, 3 H, CH), 7.45Ϫ7.55 (m, 2 H, CH) ppm. 13C NMR (50 MHz,
43 (50). C22H34O3Se (425.5): calcd. C 62.12, H 8.06; found C 62.44,
H 7.89.
CDCl3, 25 °C, TMS): δ ϭ 20.5 (2 C), 20.6 (2 C), 25.0, 43.5, 61.9,
67.8, 68.2, 71.2, 71.7, 72.7, 100.6, 128.5, 128.9, 129.3 (2 C), 135.7
(2 C), 169.3 (2 C), 170.2, 170.6, 199.7. C24H30O11Se (573.4): calcd.
C 50.27, H 5.27; found C 50.03, H 5.44.
Ethyl 2-Benzoyl-2-[3-oxo-3-(phenylseleno)propyl]pent-4-enoate (4i):
Yield 74% (0.20 g); oil. 1H NMR (200 MHz, CDCl3, 25 °C, TMS):
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δ ϭ 1.10 (t, JH,H ϭ 7.1 Hz, 3 H, CH3), 2.42 (ddd, JH,H ϭ 14.3, Se-Phenyl 3-[(Phenylsulfonyl)amino]propaneselenoate (4n): Yield
3JH,H ϭ 9.8, 3.8 Hz, 1 H, CH2), 2.45Ϫ2.65 (m, 2 H, CH2), 2.73 78% (0.33 g); oil. H NMR (200 MHz, CDCl3, 25 °C, TMS): δ ϭ
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(ddd, 2JH,H ϭ 14.3, 3JH,H ϭ 9.8, 3.3 Hz, 1 H, CH2), 2.75Ϫ2.87 (m,
2.90 (t, JH,H ϭ 6.0 Hz, 2 H, CH2), 3.20 (t, JH,H ϭ 6.0 Hz, 2 H,
3
3
3
2 H, CH2), 4.15 (q, JH,H ϭ 7.1 Hz, 2 H, CH2), 5.05Ϫ5.15 (m, 2 CH2), 5.22 (br. s, 1 H, NH), 7.15Ϫ7.65 (m, 8 H, CH), 7.74Ϫ7.93
H, CH2), 5.60 (ddt, 3JH,H ϭ 17.0, 9.9, 7.5 Hz, 1 H, CH2), 7.34Ϫ7.40
(m, 3 H, CH), 7.41Ϫ7.51 (m, 4 H, CH), 7.53Ϫ7.59 (m, 1 H, CH), 38.7, 46.8, 126.2, 126.9 (2 C), 129.1 (2 C), 129.4 (2 C), 132.7 (2 C),
7.82Ϫ7.87 (m, 2 H, CH) ppm. 13C NMR (50 MHz, CDCl3, 25 °C, 135.7 (2 C), 139.7, 199.9. FT-IR: ν˜ ϭ 3290, 1713, 1328, 1162 cmϪ1
TMS): δ ϭ 13.8, 28.0, 37.6, 42.0, 59.6, 61.1, 119.7, 126.1, 128.3 (2
GC-MS: m/z (%) ϭ 368 (3) [Mϩ], 213 (51), 185 (72), 157 (100), 91
(m, 2 H, CH) ppm. 13C NMR (50 MHz, CDCl3, 25 °C, TMS): δ ϭ
.
C), 128.6 (3 C), 128.8 (2 C), 129.3, 131.4, 132.9, 135.5, 135.7, 172.4, (15), 51 (15). C15H15NO3SSe (368.3): calcd. C 48.93, H 4.11, N
195.9, 199.0 ppm. GC-MS: m/z (%) ϭ 287 (26) [M Ϫ 157]ϩ, 241
(6), 157 (4), 105 (100), 77 (22), 55 (5). C23H24O4Se (443.4): calcd.
C 62.31, H 5.46; found C 62.12, H 5.60.
3.80; found C 49.15, H 4.23, N 3.55.
Se-Phenyl 3-({2-[(Phenylsulfonyl)amino]propanoyl}amino)propane-
selenoate (4o): Yield 51% (0.23 g); oil. 1H NMR (200 MHz, CDCl3,
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1-(Butoxymethyl)-4-oxo-4-(phenylseleno)butyl Acetate (4j): Yield
25 °C, TMS): δ ϭ 1.22 (d, JH,H ϭ 7.1 Hz, 3 H, CH3), 2.83 (t,
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56% (0.21 g); oil. H NMR (200 MHz, CDCl3, 25 °C, TMS): δ ϭ 3JH,H ϭ 5.6 Hz, 2 H, CH2), 3.41 (td, JH,H ϭ 5.6, 4.5 Hz, 2 H,
0.91 (t, 3JH,H ϭ 7.2 Hz, 3 H, CH3), 1.20Ϫ1.62 (m, 4 H, CH2), 2.08 CH2), 3.79 (dq, JH,H ϭ 7.5, 7.1 Hz, 1 H, CH), 6.08 (d, JH,H
ϭ
3
3
3
3
(s, 3 H, CH3), 1.90Ϫ2.20 (m, 2 H, CH2), 2.77 (t, JH,H ϭ 7.5 Hz,
7.5 Hz, 1 H, NH), 6.92 (t, JH,H ϭ 4.5 Hz, 1 H, NH), 7.20Ϫ7.66
2 H, CH2), 3.30Ϫ3.58 (m, 4 H, CH2), 5.02 (dq, 3JH,H ϭ 7.4, 5.0 Hz, (m, 8 H, CH), 7.80Ϫ7.94 (m, 2 H, CH) ppm. 13C NMR (50 MHz,
1 H, CH), 7.20Ϫ7.39 (m, 3 H, CH), 7.40Ϫ7.55 (m, 2 H, CH) ppm. CDCl3, 25 °C, TMS): δ ϭ 19.1, 35.2, 46.5, 52.6, 125.9, 127.1 (2 C),
13C NMR (50 MHz, CDCl3, 25 °C, TMS): δ ϭ 13.8, 19.1, 20.9, 129.1 (3 C), 129.4, 132.8 (2 C), 135.7 (2 C), 139.7, 171.7, 195.1.
26.3, 31.5, 43.2, 70.8, 71.3 (2 C), 127.8, 128.8, 129.2 (2 C), 135.7 (2
C), 170.1, 199.3. C17H24O4Se (371.3): calcd. C 55.00, H 6.52; found
C 55.21, H 6.89.
C18H20N2O4SSe (439.4): calcd. C 49.21, H 4.59, N 6.38; found C
49.39, H 4.41, N 4.33.
Se-Phenyl 3-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)propaneseleno-
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(1S)-1-[(Benzyloxy)methyl]-4-oxo-4-(phenylseleno)butyl Acetate ate (4p): Yield 95% (0.68 g); m.p. 90Ϫ93 °C. H NMR (200 MHz,
(4k): Yield 51% (0.31 g); oil. [α]2D5ϭ Ϫ2.82 (c ϭ 3.94 in CHCl3). 1H
CDCl3, 25 °C, TMS): δ ϭ 3.10 (t, 3JH,H ϭ 7.0 Hz, 2 H, CH2), 3.99
NMR (200 MHz, CDCl3, 25 °C, TMS): δ ϭ 2.00 (s, 3 H, CH3), (t, 3JH,H ϭ 7.0 Hz, 2 H, CH2), 7.25Ϫ7.40 (m, 3 H, CH), 7.40Ϫ7.54
1.90Ϫ2.04 (m, 2 H, CH2), 2.70 (t, 3JH,H ϭ 7.5 Hz, 2 H, CH2), 3.44 (m, 2 H, CH), 7.57Ϫ7.63 (m, 2 H, CH), 7.44Ϫ7.88 (m, 2 H, CH)
2
3
2
(dd, JH,H ϭ 10.5, JH,H ϭ 4.7 Hz, 1 H, CH2), 3.47 (dd, JH,H
ϭ
ppm. 13C NMR (50 MHz, CDCl3, 25 °C, TMS): δ ϭ 33.6, 44.9,
123.0 (2 C), 128.4, 128.7, 129.1 (2 C), 131.7 (2 C), 133.8 (2 C),
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2
10.5, JH,H ϭ 5.1 Hz, 1 H, CH2), 4.44 (d, JH,H ϭ 12.1 Hz, 1 H,
2
CH2), 4.50 (d, JH,H ϭ 12.1 Hz, 1 H, CH2), 4.94Ϫ5.05 (m, 1 H, 135.4 (2 C), 167.4 (2 C), 197.0. FT-IR: ν˜ ϭ 3030, 1775, 1716, 1396
CH), 7.15Ϫ7.35 (m, 8 H, CH), 7.40Ϫ7.50 (m, 2 H, CH) ppm. 13C
NMR (50 MHz, CDCl3, 25 °C, TMS): δ ϭ 21.0, 26.3, 43.2, 70.5,
cmϪ1. GC-MS: m/z (%) ϭ 202 (65) [M Ϫ 157]ϩ, 160 (100), 77 (11).
C17H13NO3Se (358.2): calcd. C 57.00, H 3.66, N 3.91; found C
71.3, 73.1, 126.2, 127.6, 127.7, 128.4, 128.6, 128.8, 128.9, 129.3 (2 57.19, H 3.80, N 3.68.
C), 129.7, 135.7 (2 C), 137.7, 170.4. C20H22O4Se (405.3): calcd. C
Se-Phenyl 3-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)butaneseleno-
59.27, H 5.47; found C 59.46, H 5.61.
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ate (4q): Yield 72% (0.27 g); m.p. 76Ϫ78 °C. H NMR (200 MHz,
(1S)-1-[(Benzyloxy)methyl]-5-oxo-5-(phenylseleno)pentyl Acetate CDCl3, 25 °C, TMS): δ ϭ 1.55 (d, 3JH,H ϭ 7.0 Hz, 3 H, CH3), 3.24
(4l): Yield 60% (0.25 g); oil. [α]2D0ϭ Ϫ3.07 (c ϭ 1.50 in CHCl3). H
NMR (200 MHz, CDCl3, 25 °C, TMS): δ ϭ 1.58Ϫ1.80 (m, 4 H,
(dd, JH,H ϭ 16.0, JH,H ϭ 5.7 Hz, 1 H, CH2), 3.66 (dd, JH,H
ϭ
1
2
3
2
3
3
16.0, JH,H ϭ 8.8 Hz, 1 H, CH2), 4.91 (dqd, JH,H ϭ 8.8, 7.0,
5.7 Hz, 1 H, CH), 7.30Ϫ7.55 (m, 5 H, CH), 7.65Ϫ7.95 (m, 4 H,
CH2), 2.08 (s, 3 H, CH3), 2.64Ϫ2.78 (m, 2 H, CH2), 3.50 (d,
3JH,H ϭ 8.3 Hz, 2 H, CH2), 4.45 (d, JH,H ϭ 12.1 Hz, 1 H, CH2), CH) ppm. 13C NMR (50 MHz, CDCl3, 25 °C, TMS): δ ϭ 18.8,
2
2
4.55 (d, JH,H ϭ 12.1 Hz, 1 H, CH2), 4.95Ϫ5.10 (m, 1 H, CH),
43.5, 50.2, 123.3 (2 C), 126.0, 129.0, 129.4 (2 C), 131.9 (2 C), 134.0
7.25Ϫ7.45 (m, 8 H, CH), 7.35Ϫ7.55 (m, 2 H, CH) ppm. 13C NMR (2 C), 135.7 (2 C), 167.9 (2 C), 197.6 ppm. GC-MS: m/z (%) ϭ 216
(50 MHz, CDCl3, 25 °C, TMS): δ ϭ 20.1, 21.1, 29.9, 46.9, 70.7,
(48) [M Ϫ 157]ϩ, 174 (100), 130 (20). C18H15NO3Se (372.3): calcd.
71.9, 73.1, 126.3, 127.5, 127.6 (2 C), 128.3 (2 C), 128.8, 129.3 (2 C 58.08, H 4.06, N 3.76; found C 58.33, H 4.19, N 3.55.
C), 135.7 (2 C), 137.9, 170.6, 199.8. C21H24O4Se (419.4): calcd. C
Se-Phenyl 3-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)octaneseleno-
60.15, H 5.77; found C 60.01, H 5.92.
ate (4r): Yield 85% (0.29 g); oil. 1H NMR (200 MHz, CDCl3, 25
Se-Phenyl 4-[(2,3,4,6-Tetra-O-acetyl-β-
butaneselenoate (4m): Yield 62% (0.23 g); oil. H NMR (200 MHz,
D
-glucopyranosyl)oxy]- °C, TMS): δ ϭ 0.7Ϫ0.9 (m, 3 H, CH3), 1.1Ϫ1.4 (m, 6 H, CH2),
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1.79Ϫ1.80 (m, 1 H, CH2), 1.95Ϫ2.25 (m, 1 H, CH2), 3.18 (dd,
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Eur. J. Org. Chem. 2004, 3447Ϫ3458
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim