The Journal of Organic Chemistry
Article
25.9, 25.7, 23.9. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C15H22O2Na, 257.1512; found, 257.1511.
product was purified by flash chromatography on silica gel (eluent:
PE) to give 17 (2.75 g, 17.6 mmol, 88%) as a colorless oil. E/Z =
0.55:0.45. H NMR (600 MHz, CDCl3): δ 6.27 (d, J = 12.6 Hz,
1
(Table 3, Entry 10): The above general procedure was followed
using the corresponding aldehyde (3.56 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE/EtOAc = 20:1) to give 12 (3.22 g, 15.6 mmol, 78%) as a slightly
yellow oil. E/Z = 2:1. 1H NMR (600 MHz, CDCl3): δ 7.54−7.14 (m,
5H), 6.30 (d, J = 12.6 Hz, 0.67H), 5.89 (d, J = 6.1 Hz, 0.33H), 4.72
(dt, J = 12.6, 7.2 Hz, 0.67H), 4.55 (d, 2H), 4.36 (dt, J = 6.1, 7.1 Hz,
0.33H), 3.77−3.09 (m, 5H), 2.21−2.09 (m, 0.66H), 2.08−2.00 (m,
1.34H), 1.73−1.54 (m, 2H). 13C{1H} NMR (151 MHz, CDCl3): δ
147.5, 146.6, 138.8, 128.5, 128.4, 128.4, 127.9, 127.7, 127.6, 127.5,
106.3, 102.5, 73.0, 72.3, 70.2, 69.7, 59.5, 56.0, 30.9, 30.0, 24.4, 20.7.
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C13H18O2Na, 229.1199;
found, 229.1198.
(Table 3, Entry 11): The above general procedure was followed
using the corresponding aldehyde (4.57 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE/EtOAc = 25:1) to give 13 (4.10 g, 16 mmol, 80%) as a colorless
oil. E/Z = 0.64:0.36. 1H NMR (600 MHz, CDCl3): δ 6.26 (d, J = 12.6
Hz, 0.64H), 5.84 (d, J = 6.2 Hz, 0.36H), 4.82 (t, J = 4.8 Hz, 1H), 4.71
(dt, J = 12.6, 7.3 Hz, 0.64H), 4.31 (dt, J = 7.2, 7.2 Hz, 0.36H), 3.95 (t,
J = 6.9 Hz, 2H), 3.83 (t, J = 6.9 Hz, 2H), 3.56 (s, 1.08H), 3.48 (s,
1.92H), 2.02 (dt, J = 6.9, 6.9 Hz, 0.72H), 1.89 (dt, J = 6.9, 6.9 Hz,
1.28H), 1.66−1.61 (m, 2H), 1.43−1.25 (m, 14H). 13C{1H} NMR
(151 MHz, CDCl3): δ 147.0, 146.0, 107.3, 104.8, 103.3, 64.9 (2C),
59.6, 56.0, 34.0, 30.9, 29.9, 29.7, 29.6, 29.6, 29.6, 29.4, 29.1, 27.8,
24.2, 24.0. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C15H28O3Na, 279.1931; found, 279.1932.
0.55H), 5.85 (d, J = 6.2 Hz, 0.45H), 4.72 (dt, J = 12.6, 7.3 Hz,
0.55H), 4.33 (dt, J = 7.2, 7.2 Hz, 0.45H), 3.57 (s, 1.35H), 3.49 (s,
1.65H), 2.04 (dt, J = 7.0, 7.0 Hz, 0.9 H), 1.91 (dt, J = 6.9, 6.9 Hz,
1.1H), 1.27−1.32 (m, 10H), 0.86−0.89 (m, 3H). 13C{1H} NMR
(151 MHz, CDCl3): δ 147.1, 146.1, 107.4, 103.4, 59.5, 56.0, 32.1,
32.0, 31.0, 30.0, 29.4, 29.3 (2C), 29.1, 27.8, 24.0, 22.8 (2C), 14.2
(2C).15a
(Table 3, Entry 16): The above general procedure was followed
using the corresponding aldehyde (3.69 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE) to give 18 (3.70 g, 17.4 mmol, 87%) as a colorless oil. E/Z = 1:1.
1H NMR (600 MHz, CDCl3): δ 6.27 (d, J = 12.6 Hz, 0.5H), 5.85 (d, J
= 6.2 Hz, 0.5H), 4.72 (dt, J = 12.6, 7.0 Hz, 0.5H), 4.33 (dt, J = 6.2, 6.2
Hz, 0.5H), 3.56 (s, 1.5H), 3.49 (s, 1.5H), 2.05 (dt, J = 7.2, 7.2 Hz,
1H), 1.91 (dt, J = 7.2, 7.2 Hz, 1H), 1.30−1.23 (m, 18H), 0.88 (t, J =
6.9 Hz, 3H). 13C{1H} NMR (151 MHz, CDCl3): δ 147.1, 146.1,
107.4, 103.4, 59.5, 56.0, 32.1, 31.0, 30.0, 29.9, 29.8, 29.7, 29.5, 29.5,
29.2, 27.8, 24.0, 22.8, 14.2.5b
(Table 3, Entry 17): The above general procedure was followed
using the corresponding aldehyde (4.81 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE) to give 19 (4.51 g, 16.8 mmol, 84%) as a colorless oil. E/Z =
1
0.67:0.33. H NMR (600 MHz, CDCl3): δ 6.27 (d, J = 12.6 Hz,
0.67H), 5.85 (d, J = 6.2 Hz, 0.33H), 4.73 (dt, J = 12.6, 7.2 Hz,
0.67H), 4.35 (dt, J = 7.2, 7.2 Hz, 0.33H), 3.49 (s, 1H), 3.31 (s, 2H),
2.04 (dt, J = 6.3, 1 Hz, 0.66H), 1.90 (dt, J = 6.3, 1.2 Hz, 1.34H),
1.42−1.22 (m, 26H), 0.88 (t, J = 7.0 Hz, 3H). 13C{1H} NMR (151
MHz, CDCl3): 147.0, 146.0, 107.4, 103.4, 59.6, 56.0, 32.1, 31.0, 30.0,
29.9, 29.8, 29.7, 29.5, 29.5, 29.2, 27.8, 24.0, 22.9, 14.3. HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C18H37O, 269.2839; found, 269.2836.
(Table 3, Entry 18): The above general procedure was followed
using the corresponding aldehyde (3.37 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE) to give 20 (3.10 g, 15.8 mmol, 79%) as a colorless oil. E/Z =
0.6:0.4. 1H NMR (600 MHz, CDCl3): δ 6.27 (d, J = 12.6 Hz, 0.6H),
5.86 (dd, J = 6.2, 6.2 Hz, 0.4H), 5.84−5.77 (m, 1H), 5.04−4.96 (m,
1H), 4.95−4.88 (m, 1H), 4.73 (dt, J = 12.6, 7.3 Hz, 0.6H), 4.33 (dd, J
= 13.6, 7.3 Hz, 0.4H), 3.57 (s, 1.2H), 3.50 (s, 1.8H), 2.10−1.97 (m,
2.8H), 1.97−1.83 (m, 1.2H), 1.46−1.20 (m, 12H). 13C{1H} NMR
(151 MHz, CDCl3): δ 147.1, 146.1, 139.4, 139.4, 114.2, 114.2, 107.3,
103.4, 59.6, 56.0, 34.0, 30.9, 30.0, 29.6, 29.6, 29.4, 29.3, 29.2, 29.1,
27.8, 24.0.15b
(Table 3, Entry 12): The above general procedure was followed
using the corresponding aldehyde (5.17 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE) to give 14 (4.126 g, 14.4 mmol, 72%) as a slightly yellow oil. E/Z
1
= 0.7:0.3. H NMR (600 MHz, CDCl3): δ 6.27 (d, J = 12.6 Hz,
0.7H), 5.85 (dt, J = 6.2, 1.3 Hz, 0.3H), 4.72 (dt, J = 12.7, 7.3 Hz,
0.7H), 4.33 (dt, J = 7.3, 7.3 Hz, 0.3H), 3.59 (t, J = 6.6 Hz, 1.4H), 3.57
(t, J = 6.6 Hz, 0.6H), 3.49 (s, 2.1H), 3.31 (s, 0.9H), 2.08−2.00 (m,
0.6H), 1.93−1.88 (m, 1.4H), 1.52−1.47 (m, 2H), 1.35−1.24 (m,
8H), 0.89 (s, 9H), 0.04 (s, 6H). 13C{1H} NMR (151 MHz, CDCl3):
δ 147.1, 146.1, 107.3, 103.4, 63.5, 59.6, 56.0, 52.7, 33.0, 33.0, 30.9,
29.9, 29.6, 29.4, 29.1, 27.8, 26.1, 25.9 (3C), 25.9, 25.8, 24.8, 24.0,
22.2, 18.5, −5.1 (2C). HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C16H34O2SiNa, 309.2220; found, 309.2220.
(Table 3, Entry 13): The above general procedure was followed
using the corresponding aldehyde (2.88 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE/EtOAc = 5:1) to give 15 (2.65 g, 15.4 mmol, 77%) as a slightly
orange oil. E/Z = 0.55:0.45. 1H NMR (600 MHz, CDCl3): δ 6.25 (d,
J = 12.6 Hz, 0.55H), 5.84 (d, J = 6.6 Hz, 0.45H), 4.71 (dt, J = 12.7,
7.3 Hz, 0.55H), 4.31 (dt, J = 7.2, 7.2 Hz, 0.45H), 3.61 (t, J = 6.7 Hz,
2H), 3.55 (s, 1.35H), 3.48 (s, 1.65H), 2.03 (dt, J = 12.6, 6.6 Hz,
0.9H), 1.89 (dt, J = 12.6, 6.6 Hz, 1.1H), 1.62−1.50 (m, 3H), 1.39−
1.24 (m, 8H). 13C{1H} NMR (151 MHz, CDCl3): δ 147.0, 146.1,
107.2, 103.3, 63.1, 59.5, 56.0, 32.9, 30.8, 29.8, 29.4, 29.3, 29.3, 29.0,
27.7, 25.8, 25.8, 23.9. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C9H16O2Na, 195.1356; found, 195.1353.
(Table 3, Entry 14): The above general procedure was followed
using the corresponding aldehyde (2.84 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE) to give 16 (2.97 g, 15 mmol, 75%) as a colorless oil. E/Z =
0.59:0.41. 1H NMR (600 MHz, CDCl3): δ 6.26 (d, J = 12.6, 1.18H),
5.85 (d, J = 7.2, 0.82H), 4.72 (dt, J = 12.6, 7.2 Hz, 1.18H), 4.33 (dt, J
= 7.2, 7.2 Hz, 0.82H), 3.56 (s, 2.46H), 3.49 (s, 3.54H), 2.04 (dt, J =
7.2, 7.2 Hz, 1.64H), 1.90 (dt, J = 7.2, 7.2 Hz, 2.36H), 1.36−1.24 (m,
8H). 13C{1H} NMR (151 MHz, CDCl3): δ 147.1, 147.1, 146.1, 146.1,
107.3, 107.3, 103.4, 103.4, 59.6, 56.0, 30.9, 30.9, 30.0, 29.9, 29.3, 29.2,
29.0, 29.0, 27.8, 24.0, 24.0. HRMS (ESI-TOF) m/z: [M + Na]+ calcd
for C12H22O2Na, 221.1512; found, 221.1511.
(Table 3, Entry 19): The above general procedure was followed
using the corresponding aldehyde (5.05 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE) to give 21 (4.54 g, 16.2 mmol, 81%) as a colorless oil. E/Z =
1
0.55:0.45. H NMR (600 MHz, CDCl3): δ 6.27 (d, J = 12.6 Hz,
0.55H), 5.86 (dt, J = 6.2, 1.4 Hz, 0.45H), 5.41−5.28 (m, 2H), 4.73
(dt, J = 12.6, 7.3 Hz, 0.55H), 4.33 (dt, J = 7.3, 7.3 Hz, 0.45H), 3.57 (s,
1.35H), 3.50 (s, 1.65H), 2.09−1.97 (m, 4.9H), 1.91 (td, J = 6.6 Hz,
1.1H), 1.40−1.22 (m, 20H), 0.89 (t, J = 7.1 Hz, 3H). 13C{1H} NMR
(151 MHz, CDCl3): δ 147.1, 146.1, 130.1, 130.1, 130.0, 130.0, 107.4,
103.5, 59.6, 56.0, 32.1, 31.0, 30.0, 29.9, 29.8, 29.7, 29.7, 29.47, 29.2,
27.8, 27.4, 27.1, 24.0, 22.5, 14.1.15c
(Table 3, Entry 20): The above general procedure was followed
using the corresponding aldehyde (2.85 g, 20 mmol). The crude
product was purified by flash chromatography on silica gel (eluent:
PE) to give 22 (2.52 g, 14.8 mmol, 74%) as a colorless oil. E/Z =
1
0.64:0.36. H NMR (600 MHz, CDCl3): δ 6.25 (d, J = 12.6 Hz,
0.64H), 5.90 (d, J = 6.2 Hz, 0.36H), 4.70 (dt, J = 12.7, 7.6 Hz,
0.64H), 4.33 (dd, J = 13.9, 7.1 Hz, 0.36H), 3.56 (s, 1.08H), 3.50 (s,
1.92H), 2.07−1.99 (m, 0.36H), 1.95−1.84 (m, 1H), 1.79−1.71 (m,
0.64H), 1.55−1.44 (m, 1H), 1.30−1.20 (m, 1H), 1.06−0.97 (m, 1H),
0.94−0.85 (m, 12H). 13C{1H} NMR (151 MHz, CDCl3): δ 147.8,
146.7, 106.0, 101.8, 59.5, 56.0, 50.6, 50.4, 37.5, 33.5, 31.2, 30.4, 30.2,
29.9, 22.6, 22.5. HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C11H23O, 171.1743; found, 171.1743.
(Table 3, Entry 15): The above general procedure was followed
using the corresponding aldehyde (2.56 g, 20 mmol). The crude
5468
J. Org. Chem. 2021, 86, 5463−5476