Page 11 of 18
The Journal of Organic Chemistry
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MHz, CDCl3) δ 8.00–7.97 (m, 1H), 7.83–7.79 (m, 1H),
127.7 (d, J = 3.0 Hz), 125.9, 125.8, 125.8, 125.6,
116.7 (d, J = 18.0 Hz), 72.5 (d, J = 21.0 Hz), 66.9 (d,
J = 3.0 Hz), 39.9 (d, J = 13.0 Hz), -4.1; HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C36H46O6Si2Na
653.2731; found 653.2722.
7.71 (d, J = 8.4 Hz, 1H), 7.47–7.43 (m, 2H),
7.40–7.36 (m, 1H), 7.25–7.17 (m, 4H), 6.84 (d, J =
6.8 Hz, 2H), 5.45 (d, J = 1.2 Hz, 1H), 5.22 (d, J = 2.0
Hz, 1H), 4.67 (d, J = 12.0 Hz, 1H), 3.94 (d, J = 12.0
Hz, 1H), 3.29 (d, J = 14.0 Hz, 1H), 3.03 (d, J = 14.4
Hz, 1H), 2.93 (s, 1H), 0.88 (t, J = 8.0 Hz, 9H),
0.65–0.51 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3)
δ 177.0, 143.8, 140.7, 134.78, 133.6, 131.1, 128.4,
128.4, 128.2, 128.1, 127.5, 126.0, 125.8, 125.7, 125.6,
125.2, 120.0, 72.8, 66.9, 43.0, 7.4, 1.8; HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C28H34O3SiNa
469.2175; found 469.2167.
Benzyl (Z)-2-hydroxy-4-phenyl-2-(triethylsilyl)hex
-4-enoate (3af): Isolated by column chromatography
(EtOAc/petroleum ether = 1:80); yellow oil (33.6 mg,
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82% yield); H NMR (400 MHz, CDCl3) δ 7.34–7.29
(m, 3H), 7.25–7.20 (m, 4H), 7.19–7.15 (m, 3H),
5.80–5.75 (dd, J = 6.8, 13.6 Hz, 1H), 4.73 (d, J = 12.4
Hz, 1H), 3.88 (d, J = 12.4 Hz, 1H), 3.15 (d, J = 13.6,
Hz, 1H), 3.06 (d, J = 14.0 Hz, 1H), 2.76 (s, 1H), 1.80
(d, J = 6.8 Hz, 3H), 0.94 (t, J = 8.0 Hz, 9H),
0.73–0.60 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3)
δ 177.2, 143.4, 135.9, 135.2, 129.0, 128.6, 128.3,
128.2, 127.9, 127.4, 126.5, 72.9, 66.7, 35.4, 15.0, 7.5,
2.0; HRMS (ESI-TOF)m/z: [M + Na]+ calcd for
C25H34O3SiNa 433.2175; found 433.2174.
Benzyl 2-hydroxy-4-(thiophen-2-yl)-2-(triethylsilyl)
pent-4-enoate
(3ac):
Isolated
by
column
chromatography (EtOAc/petroleum ether = 1:60); pale
yellow oil (36.2 mg, 90% yield); 1H NMR (400 MHz,
CDCl3) δ 7.38–7.29 (m, 5H), 7.16–7.10 (m, 1H), 7.01
(d, J = 3.2 Hz, 1H), 6.95–6.90 (m, 1H), 5.40 (s, 1H),
5.06 (d, J = 12.0 Hz, 1H), 4.93 (s, 1H), 4.79 (d, J =
12.0 Hz, 1H), 3.09 (d, J = 14.4 Hz, 1H), 2.92 (d, J =
14.4 Hz, 1H), 2.89 (s, 1H), 0.98 (t, J = 8.0 Hz, 9H),
0.73–0.63 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3)
δ 177.0, 145.8, 137.0, 135.1, 128.9, 128.5, 128.5,
127.1, 124.6, 124.7, 114.7, 73.4, 67.2, 40.7, 7.5, 2.0;
Benzyl (Z)-2-hydroxy-4-phenyl-2-(triethylsilyl)hept
-4-enoate (3ag): Isolated by column chromatography
(EtOAc/petroleum ether = 1:60); yellow oil (36.0 mg,
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85% yield); H NMR (400 MHz, CDCl3) δ 7.33–7.29
(m, 3H), 7.25–7.23 (m, 4H), 7.20–7.14 (m, 3H), 5.66
(t, J = 7.2 Hz, 1H), 4.71 (d, J = 12.0 Hz, 1H), 3.84 (d,
J = 12.0 Hz, 1H), 3.12 (d, J =14.0 Hz, 1H), 3.06 (d, J
=14.0Hz, 1H), 2.76 (s, 1H), 2.27–2.19 (m, 2H), 1.02 (t,
J = 7.6 Hz, 3H), 0.94 (t, J = 8.0 Hz, 9H), 0.70–0.60
(m, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ 177.2,
143.9, 137.0, 135.2, 134.0, 128.57, 128.59, 128.2,
127.9, 127.5, 126.5, 72.4, 66.7 35.6, 22.5, 14.3 7.5,
2.0; HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C26H36O3SiNa 447.2331; found 447.2323.
HRMS (ESI-TOF) m/z: [M
+
Na]+ calcd for
C22H30O3SSiNa 425.1583; found 425.1578.
Benzyl 2-hydroxy-4-(3-(prop-1-en-2-yl)phenyl)-2-
(triethylsilyl)pent-4-enoate (3ad): Isolated by
column chromatography (EtOAc/petroleum ether =
1:60); pale yellow oil (35.8 mg, 82% yield); Rf 0.13
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(EtOAc/petroleum ether, 1:80). H NMR (400 MHz,
CDCl3) δ 7.42 (s, 1H), 7.35–7.28 (m, 4H), 7.25–7.17
(m, 4H), 5.36 (s, 1H), 5.25 (d, J = 1.6 Hz, 1H), 5.08 (t,
J = 0.8 Hz, 2H), 4.88 (d, J = 12.0 Hz, 1H), 4.38 (d, J =
12.0 Hz, 1H), 3.17 (d, J = 14.0 Hz, 1H), 2.92 (d, J =
14.4 Hz, 1H), 2.83 (s, 1H), 2.12 (s, 3H), 0.94 (t, J =
8.0 Hz, 9H), 0.71–0.63(m, 6H); 13C{1H} NMR (100
MHz, CDCl3) δ 177.0, 144.2, 143.2, 142.2, 141.0,
135.1, 128.7, 128.4, 128.3, 127.9, 126.0, 124.5, 124.2,
116.9, 112.6, 72.9, 67.0, 40.9, 21.8, 7.5, 1.9; HRMS
(ESI-TOF) m/z: [M + Na]+ calcd for C27H36O3SiNa
459.2331; found 459.2329.
Benzyl 2-hydroxy-3-(1H-inden-3-yl)-2-(triethyl
silyl)propanoate (3ai): Isolated by column
chromatography (EtOAc/petroleum ether = 1:60);
colorless oil (37.9 mg, 93% yield); 1H NMR (400
MHz, CDCl3) δ 7.41–7.37 (m, 2H), 7.34–7.31 (m, 3H),
7.30–7.26 (m, 2H), 7.24–7.14 (m, 2H), 6.13 (s, 1H),
5.08 (d, J = 12.0 Hz, 1H), 5.00 (d, J = 12.0 Hz, 1H),
3.22 (s, 2H), 3.17 (d, J = 18.8 Hz, 1H), 3.01 (d, J =
14.8 Hz, 1H), 2.88 (s, 1H), 1.02 (t, J = 8.0 Hz, 9H),
0.78–0.72 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3)
δ 177.4, 145.8, 143.9, 139.4, 135.2, 131.2, 128.9,
128.5, 125.8, 124.4, 123.5, 119.7, 74.1, 67.2, 38.0,
32.9, 7.6, 2.0; HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C25H32O3SiNa 431.2018; found 431.2019.
Dibenzyl 4,4'-(1,3-phenylene)bis(2-hydroxy-2-(tri
methylsilyl)pent-4-enoate) (3ae): Isolated by column
chromatography (EtOAc/petroleum ether = 1:80);
colorless oil (45.4 mg, 72% yield); 1H NMR (400
MHz, CDCl3) δ 7.30–7.23 (m, 6H), 7.20–7.11 (m, 8H),
5.21–5.19 (dd, J = 1.2, 4.4 Hz, 2H), 5.04 (d, J = 2.8
Hz, 2H), 4.95–4.90 (dd, J = 6.0, 12.0 Hz, 2H),
4.48–4.39 (dd, J = 12.4, 23.2 Hz, 2H), 3.09 (d, J =
14.0 Hz, 2H), 2.82–2.77 (m, 4H), 0.00 (d, J = 2.4 Hz,
18H); 13C{1H} NMR (100 MHz, CDCl3) δ 177.9,
144.3 (d, J = 4.0 Hz), 142.0, 135.3 (d, J = 3.0 Hz),
128.7 (d, J = 2.0 Hz), 128.4, 128.3 (d, J = 2.0 Hz),
Benzyl 3-(3,4-dihydronaphthalen-1-yl)-2-hydroxy-
2-(triethylsilyl)propanoate (3aj): Isolated by column
chromatography (EtOAc/petroleum ether = 1:60);
colorless oil (34.2 mg, 81% yield); Rf 0.15
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(EtOAc/petroleum ether, 1:60). H NMR (400 MHz,
CDCl3) δ 7.36–7.25 (m, 6H), 7.13–7.08 (m, 3H), 5.80
(t, J = 4.4 Hz, 1H), 4.97 (d, J = 12.0Hz, 1H), 4.78 (d,
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