1950
S. D. Halperin et al.
PAPER
H), 2.88–2.95 (m, 2 H), 2.73–2.85 (m, 4 H), 1.78–1.87 (m, 1 H),
(3S*,4R*)-3-Chloro-4-hydroxy-2-methylpentadecan-6-one (16)
1.58–1.68 (m, 1 H), 1.38–1.45 (m, 1 H), 0.95 (t, J = 7.2 Hz, 3 H).
Isolated as a colorless solid (76% yield); mp 45–50 °C.
13C NMR (100 MHz, CDCl3): d = 210.5, 140.6, 128.6, 128.3, 126.3,
IR (thin film): 3688, 3054, 2685, 1694 cm–1.
70.9, 65.8, 45.19, 45.17, 35.8, 29.5, 19.6, 13.5.
1H NMR (400 MHz, CDCl3): d = 4.14–4.06 (m, 1 H), 3.78 (dd,
J = 3.7, 8.7 Hz, 1 H), 3.49 (d, J = 5.2 Hz, 1 H), 2.99 (dd, J = 2.4,
17.8 Hz, 1 H), 2.71 (dd, J = 8.4, 17.8 Hz, 1 H), 2.47 (t, J = 7.5 Hz,
2 H), 2.43–2.33 (m, 1 H), 1.64–1.55 (m, 2 H), 1.34–1.22 (m, 12 H),
1.03 (d, J = 6.6 Hz, 3 H), 0.98 (d, J = 6.6 Hz, 3 H), 0.89 (t, J = 6.6
Hz, 3 H).
HRMS: m/z calcd for C15H21ClO2: 291.1122 (M + Na); found:
291.1131 (M + Na).
(5R*,6S*)-6-Chloro-5-hydroxy-7-methyl-1-phenyloctan-3-one
(12)
Isolated as a colorless solid (90% yield); mp 30–35 °C.
IR (thin film): 3943, 3688, 2685, 1704, 1421 cm–1.
13C NMR (100 MHz, CDCl3): d = 212.9, 71.4, 69.1, 45.6, 43.8, 31.8
29.4, 29.3, 29.2, 29.1, 29.0, 23.6, 22.6, 20.7, 15.7, 14.1.
1H NMR (400 MHz, CDCl3): d = 7.28–7.36 (m, 2 H), 7.17–7.27 (m,
3 H), 4.09–4.19 (m, 1 H), 3.77 (dd, J = 3.6, 8.4 Hz, 1 H), 3.40 (d,
J = 5.4 Hz, 1 H), 3.02–2.80 (m, 5 H), 2.73 (dd, J = 8.4, 17.8 Hz, 1
H), 2.36 (m, 1 H), 1.03 (d, J = 6.8 Hz, 3 H), 0.98 (d, J = 6.8 Hz, 3
H).
HRMS: m/z calcd for C16H31ClO2: 291.2083 (M + H); found:
291.2085 (M + H).
(4S*,5R*)-4-Chloro-5-hydroxyhexadecan-7-one (17)
Isolated as a white solid (74% yield); mp 35–38 °C.
13C NMR (100 MHz, CDCl3): d = 211.3, 140.5, 128.5, 128.2, 126.2,
IR (thin film): 3435, 2923, 2859, 1708, 1458, 1374, 1068, 754 cm–1.
71.4, 69.0, 46.0, 45.1, 29.4, 29.1, 20.6, 15.8.
1H NMR (600 MHz, CDCl3): d = 4.10 (m, 1 H), 3.92 (m, 1 H), 3.32
(d, J = 4.8 Hz, 1 H), 2.82 (dd, J = 2.9, 17.6 Hz, 1 H), 2.75 (dd,
J = 8.5, 17.6 Hz, 1 H), 2.46 (t, J = 7.5 Hz, 2 H), 1.85 (m, 1 H), 1.68–
1.55 (m, 4 H), 1.42 (m, 1 H), 1.33–1.21 (m, 12 H), 0.94 (t, J = 7.3
Hz, 3 H), 0.88 (t, J = 7.0 Hz, 3 H).
HRMS: m/z calcd for C15H21ClO2: 291.1119 (M + Na); found:
291.1122 (M + Na).
(5R*,6S*)-6-Chloro-5-hydroxy-1,7-diphenylheptan-3-one (13)
Isolated as a colorless solid (75% yield); mp 56–60 °C.
IR (thin film): 3463, 3028, 2924, 2360, 1704, 1491, 1455, 698 cm–1.
13C NMR (150 MHz, CDCl3): d = 212.3, 71.2, 65.9, 45.0, 44.1, 36.1,
32.1, 29.6, 29.6, 29.5, 29.3, 23.8, 22.9, 19.8, 14.3, 13.7.
1H NMR (400 MHz, CDCl3): d = 7.36–7.16 (m, 10 H), 4.15–4.07
(m, 2 H), 3.41 (d, J = 4.7 Hz, 1 H), 3.30 (dd, J = 3.8, 15 Hz, 1 H),
2.98–2.75 (m, 7 H).
HRMS: m/z calcd for C16H31ClO2: 313.1905 (M + Na); found:
313.1901 (M + Na).
(2S*,3R*)-2-Chloro-3-hydroxy-1-phenyltetradecan-5-one (18)
Isolated as a white solid (63% yield); mp 60.5–61.0 °C.
IR (thin film): 3349, 2916, 2849, 1698, 698 cm–1.
1H NMR (600 MHz, CDCl3): d = 7.34–7.30 (m, 2 H), 7.27–7.24 (m,
3 H), 4.12–4.07 (m, 2 H), 3.52 (d, J = 4.8 Hz, 1 H), 3.32 (dd,
J = 3.1, 14.4 Hz, 1 H), 2.95 (dd, J = 8.6, 14.4 Hz, 1 H), 2.91 (dd,
J = 2.1, 17.8 Hz, 1 H), 2.78 (dd, J = 8.1, 17.8 Hz, 1 H), 2.45 (t,
J = 7.4 Hz, 2 H), 1.58 (m, 2 H), 0.88 (t, J = 7.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 210.7, 129.5, 128.6, 128.4, 128.3,
126.9, 126.3, 70.5, 65.5, 45.2, 45.1, 40.0, 29.5.
HRMS: m/z calcd for C19H21ClO2: 317.1300 (M + H); found:
317.1303 (M + H).
(3R*,4S*)-4-Chloro-3-hydroxy-5-methyl-1-phenylhexan-1-one
(14)
Isolated as a colorless solid (77% yield); mp 110–115 °C.
IR (thin film): 3507, 3066, 2930, 1968, 1663 cm–1.
13C NMR (150 MHz, CDCl3): d = 212.5, 137.5, 129.8, 128.6, 127.1,
70.8, 65.8, 45.0, 44.1, 40.3, 32.1, 29.6, 29.6, 29.5, 29.3, 23.8, 22.9,
14.3.
1H NMR (400 MHz, CDCl3): d = 8.0 (d, J = 8.0 Hz, 2 H), 7.62 (tt,
J = 1.2, 7.4 Hz, 1 H), 7.51 (t, J = 8.4 Hz, 2 H), 4.31 (ddt, J = 2.5,
4.9, 8.6 Hz, 1 H), 3.91 (dd, J = 3.5, 8.0 Hz, 1 H), 3.64 (d, J = 4.9
Hz, 1 H), 3.61 (dd, J = 2.5, 17.9 Hz, 1 H), 3.25 (dd, J = 8.4, 17.9 Hz,
1 H), 2.52–2.44 (m, 1 H), 1.07 (d, J = 6.8 Hz, 3 H), 1.03 (d, J = 6.8
Hz, 3 H).
HRMS: m/z calcd for C20H31ClO2: 339.2085 (M + H); found:
339.2077 (M + H).
(6S*,7R*)-6-Chloro-7-hydroxynonadec-18-en-9-one (19)
Isolated as a white solid (88% yield); mp 30 °C.
IR (thin film): 3416, 2921, 2852, 1698, 1087 cm–1.
13C NMR (100 MHz, CDCl3): d = 201.1, 136.6, 133.8, 128.7, 128.2,
71.5, 69.3, 42.0, 29.0, 20.7, 15.7.
HRMS: m/z calcd for C13H17ClO2: 263.0809 (M + Na); found:
263.0809 (M + Na).
1H NMR (500 MHz, CDCl3): d = 5.80 (tdd, J = 6.5, 10.5, 17.5 Hz,
1 H), 4.98 (dd, J = 1.5, 17.5 Hz, 1 H), 4.92 (dd, J = 1.5, 10.5 Hz, 1
H), 4.09 (m, 1 H), 3.90 (ddd, J = 3.0, 6.0, 9.5 Hz, 1 H), 3.31 (d,
J = 5.5 Hz, 1 H), 2.81 (dd, J = 3.0, 9.5 Hz, 1 H), 2.74 (dd, J = 8.5,
9.5 Hz, 1 H), 2.45 (t, J = 7.5 Hz, 2 H), 1.99 (dd, J = 7.0, 15.0 Hz, 2
H), 1.88 (m, 1 H), 1.67–1.57 (m, 4 H), 1.46–1.23 (m, 15 H), 0.89 (t,
J = 7.0 Hz, 3 H).
13C NMR (125 MHz, CDCl3): d = 212.0, 139.1, 114.1, 70.9, 66.0,
44.8, 43.8, 33.81, 33.77, 31.2, 29.29, 29.26, 29.1, 29.0, 28.9, 26.0,
23.5, 22.5, 14.0.
(3R*,4S*)-4-Chloro-3-hydroxy-1-phenylheptan-1-one (15)
Isolated as a white solid (96% yield); mp 54–55 °C.
IR (thin film): 2962, 2954, 2922, 1681, 1597, 1449, 1377 cm–1.
1H NMR (600 MHz, CDCl3): d = 7.98 (d, J = 8.4 Hz, 2 H), 7.61 (tt,
J = 1.3, 7.4 Hz, 1 H), 7.49 (dt, J = 1.3, 7.4 Hz, 2 H), 4.30 (m, 1 H),
4.05 (ddd, J = 3.6, 6.6, 9.6 Hz, 1 H), 3.49 (d, J = 4.8 Hz, 1 H), 3.42
(dd, J = 2.4, 17.4 Hz, 1 H), 3.31 (dd, J = 9.0, 17.4 Hz, 1 H), 1.94
(m, 1 H), 1.76–1.63 (m, 2 H), 1.47 (m, 1 H), 0.97 (t, J = 7.2 Hz, 3
H).
HRMS: m/z calcd for C19H36ClO2: 331.2404 (M + H); found:
331.2402 (M + H).
13C NMR (150 MHz, CDCl3): d = 200.4, 136.6, 133.7, 128.7, 128.2,
(6R*,7S*)-1-(tert-Butyldimethylsilyloxy)-7-chloro-6-hydroxy-8-
phenyloctan-4-one (20)
Isolated as a clear, colorless oil (57% yield).
IR (neat): 3446, 2952, 2927, 2851, 2356, 1708, 1249, 698 cm–1.
71.1, 65.8, 41.1, 36.0, 19.6, 13.5.
HRMS: m/z calcd for C13H18ClO2: 241.0995 (M – H2O + H); found:
241.1010 (M – H2O + H).
Synthesis 2011, No. 12, 1946–1953 © Thieme Stuttgart · New York