Molecules 2020, 25, 2018
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3-(Phenylselanyl)cycloheptanone (27) [48]: Isolated as a yellow oil in 95% yield (0.082 g) without
1
purification. H NMR (200 MHz, CDCl3)
δ
= 7.70–7.50 (m, 2 H, CH), 7.40–7.30 (m, 3 H, CH), 3.50 (dddd,
J = 2.8, 4.0, 9.6, and 9.8 Hz, 1 H, CH), 2.85 (ddd, J = 0.9, 4.0, and 14.9 Hz, 1 H, CH2), 2.75 (dd, J = 9.6
and 14.9 Hz, 1 H, CH2), 2.55–2.35 (m, 2 H, CH2), 2.15–2.05 (m, 1 H, CH2) 1.86–1.44 (m, 5 H, CH2) ppm;
13C NMR (50.31 MHz, CDCl3)
δ = 211.8, 135.0, 129.1, 128.8, 128.0, 50.3, 43.9, 38.8, 37.7, 29.1, 23.7 ppm.
tert-Butyl ((1R,2S/R-4-oxo-2-(phenylselanyl)cyclopentyl)carbamate (28): Obtained as a mixture of
diastereomers (75/25) from which the major one was isolated as a yellow oil in 62% yield (0.05 g) after
flash column chromatography, eluent petroleum spirit/ethyl acetate (95:5). Rf = 0.28 (c-Hex/EtOAc 5:1);
1
ν
max= 3370, 3327, 2976, 2930, 1747, 1721, 1675, 1512, 1473, 1435, 1391, 1366, 1156, 1018 cm−1. H NMR
(400 MHz, CDCl3)
δ = 7.70–7.50 (m, 2 H, CH), 7.40–7.20 (m, 3 H, CH), 4.77 (d, 1 H, J = 5.0 Hz, NH),
4.15–4.01 (m, 1 H, CH), 3.52 (q, 1 H, J = 8.0 Hz, CH), 2.81 (dd, 1 H, J = 7.6 and 15.1 Hz, CH2), 2.77 (dd,
1 H, J = 7.3 and 14.8 Hz, CH2), 2.3 (dd, 1 H, J = 9.1 and 19.5 Hz, CH2), 2.2 (dd, 1 H, J = 8.6 and 19.6
Hz, CH2), 1.4 (s, 9 H, CH3) ppm; 13C NMR (50.31 MHz, CDCl3)
δ = 212.9, 155.1, 135.9, 129.1, 128.6,
126.4, 53.9, 45.2, 44.8, 42.2, 28.8 ppm. HRMS (ESI+) C16H21NO3NaSe (MNa+) calcd: 378.0584; found:
378.0585.
Methyl-2-(1-hydroxy-4-oxo-6-(phenylselanyl)cyclohex-2-en-1-yl)acetate (29): Isolated as a colorless oil in
29% yield (0.031g) after flash column chromatography, eluent cyclohexane/ethyl acetate (2:1). Rf = 0.22
(c-Hex/EtOAc; 2:1).
ν
max = 3454, 3056, 2985, 2955, 2925, 2852, 1732, 1685, 1619, 1577, 1521,1437, 1354,
= 7.64–7.57 (m, 2 H, CH), 7.36–7.28 (m, 3 H, CH), 6.91 (d, 1 H,
1265 cm-1. H NMR (500 MHz, CDCl3),
δ
1
J = 10.2 Hz, CH), 6.02 (d, 1 H, J = 10.2 Hz, CH), 4.18 (s, 1 H, OH), 3.74 (dd, 1 H, J = 4.3 and 14.3 Hz,
CH), 3.75 (s, 3 H, CH3), 3.30 (d, 1 H, J = 16.2 Hz, CH), 3.11 (dd, 1 H, J = 10.0 and 17.0 Hz, CH), 2.89 (dd,
1 H, J = 4.3 and 17.0 Hz, CH), 2.80 (d, 1 H, J = 16.2 Hz, CH) ppm; 13C NMR (125.77 MHz, CDCl3):
196.8, 171.9, 149.3, 135.2, 129.4, 129.1, 128.3, 128.2, 70.0, 52.22, (52.24), 50.7, 42.6, 42.5 ppm. HRMS (ESI+)
C15H16O4NaSe (MNa+) calcd: 363.0111; found: 363.0098.
3-((3-Phenylpropyl)selanyl)cyclohexanone (33): Isolated as a yellow oil in 65% yield (0.044 g) and purified
by flash column chromatography, eluent cyclohexane/ethyl acetate (9:1). Rf = 0.28 (c-Hex/EtOAc 9:1);
1
ν
max = 3026, 2928, 2858, 2362, 1714, 1602, 1495, 1454, 1274, 1122, 1030 cm-1. H NMR (400 MHz, CDCl3)
δ
= 7.28–7.25 (m, 2 H, CH), 7.19–7.15 (m, 3 H, CH), 3.18 (tt, 1 H, J = 3.9 and 10.5 Hz, CH), 2.76 (ddt, 1 H,
J = 1.6, 4.5 and 14.2 Hz, CH2), 2.70 (t, J = 7.4 Hz, 2 H, CH2), 2.60 (t, 2 H, J = 7.4 Hz, CH2), 2.47 (ddd,
1 H, J = 1.1, 10.9, and 14.2 Hz, CH2), 2.39–2.26 (m, 2 H, CH2), 2.19–2.06 (m, 2 H, CH2), 1.97 (p, 2 H,
J = 7.6 Hz, CH2), 1.83–1.64 (m, 2 H, CH2) ppm; 13C NMR (100 MHz, CDCl3)
δ = 208.9, 141.3, 128.4,
128.3, 125.9, 49.2, 40.9, 35.9, 35.8, 32.5, 32.4, 25.4, 22.5 ppm. HRMS (ESI+) C15H20ONaSe (MNa+) calcd:
319.0577; found: 319.0568.
(3S,4S/R)-3-((tert-Butyldimethylsilyl)oxy)-4-((3-phenylpropyl)selanyl)cyclopentanone (34): Isolated as a 89/11
mixture of undetermined diastereomers from which the major one has been isolated as a yellow oil in
49% yield (0.050 g) by flash column chromatography, eluent cyclohexane/ethyl acetate (95:5). Rf = 0.32
(c-Hex/EtOAc; 95:5);
ν
= 3085, 3062, 3026, 2953, 2927, 2855, 1748, 1604, 1496, 1455, 1253, 1102, 1066,
max
1026 cm-1. H NMR (400 MHz, CDCl3)
δ
= 7.29–7.26 (m, 2 H, CH), 7.20–7.15 (m, 3 H, CH), 4.41 (dt, 1
1
H, J = 2.8 and 5.4 Hz, CH), 3.45–3.39 (m, 1 H, CH), 2.92–2.85 (m, 1 H, CH2), 2.76–2.52 (m, 5 H, CH2),
2.23–2.11 (m, 2 H, CH2), 2.09–1.93 (m, 2 H, CH2), 0.85 (s, 9 H, CH3), 0.06 (s, 3 H, CH3), 0.04 (s, 3 H, CH3)
ppm; 13C NMR (100 MHz, CDCl3)
δ
= 215.0, 128.4, 128.3, 126.0, 125.91, 75.2, 46.1, 43.1, 41.0, 35.8, 31.9,
25.6, 23.7,
−
4.7,
−
4.8 ppm. HRMS (ESI+) C20H32O2NaSeSi (MNa+) calcd: 435.1234; found: 435.1235
[α]D = −17 (c = 0.5, CHCl3).
(2R)-Methyl 2-((tert-butoxycarbonyl)amino)-3-((3-oxobutyl)selanyl)propanoate (35): Isolated as a yellow
oil in 30% yield (0.021 g) after flash column chromatography, eluent cyclohexane/ethyl acetate (3:1).
Rf = 0.17 (c-Hex/EtOAc; 3:1);
ν
= 3379, 3344, 2977, 2953, 2929, 1708, 1436, 1365, 1249, 1212, 1160,
max
1050, 1007 cm-1. H NMR (600 MHz, CDCl3)
δ = 5.35 (d, 1 H, J = 6.5 Hz, NH), 4.59 (d, 1 H, J = 6.9 Hz,
1
CH), 3.74 (s, 3 H, CH3), 3.05–2.98 (m, 2 H, CH2), 2.85–2.79 (m, 2 H, CH2), 2.74–2.70 (m, 2 H, CH2), 2.14