The Journal of Organic Chemistry
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5.9, 0.6 Hz, 2H), 2.59 (s, 3H), 2.25 (s, 3H), 1.21 (t, J = 7.0 Hz, 3H);
13C NMR (75 MHz, (CD3)2CO) δ 197.4 (C), 172.1 (C), 167.8 (C),
141.3 (C), 137.2 (C), 135.2 (CH), 129.4 (CH), 129.4 (CH), 128.0
(C), 92.6 (CH), 66.4 (CH2), 59.6 (CH2), 36.5 (CH2), 26.7 (CH3),
18.9 (CH3), 14.8 (CH3); IR (neat, cm−1) 2979 (w), 2936 (w), 2895
(w), 1710 (s), 1685 (s), 1626 (s), 1268 (s), 1143 (s), 1055 (s), 818
(m), 665 (m); HRMS (ESI) calcd for C18H21BrO4 + Na+ 403.0515,
found 403.0515.
Hz, 1H), 2.66 (dt, J = 14.3, 1.2 Hz, 1H), 2.14 (dt, J = 13.6, 1.2 Hz,
1H), 1.34 (t, J = 7.2 Hz, 3H), 1.31 (d, J = 6.4 Hz, 3H), 1.30 (t, J = 7.2
Hz, 3H), 1.23 (d, J = 6.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ
171.2 (C), 171.0 (C), 136.9 (C), 136.6 (C), 135.6 (CH), 135.4 (CH),
129.2 (CH), 128.9 (CH), 128.5 (CH), 128.4 (CH), 127.5 (CH),
127.2 (CH), 127.0 (CH), 126.9 (CH), 75.4 (CH), 75.0 (CH), 69.5
(CH2), 68.3 (CH2), 60.7 (CH2), 60.5 (CH2), 56.0 (CH), 50.1 (CH),
33.9 (CH2), 27.3 (CH2), 19.4 (CH3), 14.5 (CH3), 14.5 (CH3); IR
(neat, cm−1) 2978 (m), 2849 (m), 1735 (s), 1447 (m), 1262 (m),
1150 (s), 1092 (s), 1059 (m), 749 (m), 700 (s); HRMS (ESI) calcd
for C16H20O3 + H+ 261.1485, found 261.1484.
Ethyl 3-((4-phenylbut-3-en-1-yl)oxy)but-2-enoate (40a): clear,
colorless oil (5.4 mg, 20% yield); Rf = 0.47 (hexanes/dichloro-
1
methane/ethyl ether, 10/4/1); H NMR (300 MHz, (CD3)2CO) δ
7.45−7.19 (m, 5H), 6.56 (dt, J = 15.8, 1.5 Hz, 1H), 6.34 (dt, J = 15.9,
6.8 Hz, 1H), 5.08 (s, 1H), 4.07 (q, J = 7.1 Hz, 2H), 3.97 (t, J = 6.6 Hz,
2H), 2.64 (qd, J = 6.6, 1.5 Hz, 2H), 2.26 (s, 3H), 1.21 (t, J = 7.0 Hz,
3H); 13C NMR (75 MHz, (CD3)2CO) δ 172.6 (C), 168.0 (C), 138.4
(C), 133.0 (CH), 129.4 (CH), 128.1 (CH), 126.9 (CH), 126.8 (CH),
92.1 (CH), 68.4 (CH2), 59.5 (CH2), 33.0 (CH2), 19.0 (CH3), 14.8
(CH3); IR (neat, cm−1) 3060 (w), 3028 (w), 2979 (m), 2933 (m),
1710 (s), 1624 (s), 1275 (m), 1141 (s), 1053 (s), 965 (m), 818 (m),
730 (m), 694 (m); HRMS (ESI) calcd for C16H20O3 + Na+ 283.1305,
found 283.1305.
Ethyl 3-((4-(4-methoxyphenyl)but-3-en-1-yl)oxy)but-2-enoate
(40b): clear, colorless oil (7.4 mg, 25% yield); Rf = 0.63 (hexanes/
dichloromethane/ethyl ether, 5/5/1); 1H NMR (300 MHz,
(CD3)2CO) δ 7.34 (d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H),
6.49 (dt, J = 15.8, 1.5 Hz, 1H), 6.17 (dt, J = 15.8, 6.9 Hz, 1H), 5.07 (s,
1H), 4.07 (q, J = 7.1 Hz, 2H), 3.94 (t, J = 6.6 Hz, 2H), 3.78 (s, 3H),
2.60 (qd, J = 6.7, 1.5 Hz, 2H), 2.25 (s, 3H), 1.21 (t, J = 7.0 Hz, 3H);
13C NMR (75 MHz, (CD3)2CO) δ 172.6 (C), 168.0 (C), 160.1 (C),
Ethyl 4-(4-methoxybenzylidene)-2-methyltetrahydro-2H-pyran-
3-carboxylate (42b): clear, colorless oil (4.7 mg, 16% yield, 1.00/
0.62 dr); Rf = 0.44 (hexanes/dichloromethane/ethyl ether, 5/5/1); 1H
NMR (500 MHz, CDCl3) δ 7.21 (d, J = 8.7 Hz, 2H, major), 7.16 (d, J
= 8.7 Hz, 2H, minor), 6.88 (d, J = 8.7 Hz, 2H, major), 6.86 (d, J = 8.7
Hz, 2H, minor), 6.42 (d, J = 1.2 Hz, 1H, major), 6.39 (d, J = 1.2 Hz,
1H, minor), 4.26 (q, J = 7.2 Hz, 2H, major), 4.23 (q, J = 7.2 Hz, 2H,
minor), 4.20−4.12 (m, 1H, major), 4.09 (dd, J = 10.9, 5.8 Hz, 1H,
minor), 3.82 (s, 3H, major), 3.81 (s, 3H, minor), 3.69 (qd, J = 6.4, 3.4
Hz, 1H, minor), 3.58−3.52 (m, 2H, major), 3.49 (qd, J = 6.4, 3.4 Hz,
1H, major), 3.37 (ddd, J = 12.7, 11.1, 2.8 Hz, 1H, minor), 3.17−3.08
(m, 1H, major), 3.14 (d, J = 3.2 Hz, 1H, minor), 2.90 (dddd, J = 14.3,
12.3, 6.0, 2.0 Hz, 1H, minor), 2.64 (d, J = 14.3 Hz, 1H, minor), 2.11
(d, J = 13.9 Hz, 1H, major), 1.34 (t, J = 7.2 Hz, 3H, major), 1.30 (d, J
= 6.8 Hz, 3H, minor), 1.29 (t, J = 7.2 Hz, 3H, minor), 1.23 (d, J = 6.8
Hz, 3H, major); 13C NMR (125 MHz, CDCl3) δ 171.4 (C, minor),
171.2 (C, major), 158.7 (C, major), 158.6 (C, minor), 134.1 (C,
minor), 133.9 (C, major), 130.4 (CH, minor), 130.2 (CH, major),
129.4 (C, minor), 129.1 (C, major), 127.1 (CH, minor), 126.8 (CH,
major), 114.0 (CH, major), 113.8 (CH, minor), 75.4 (CH, minor),
74.9 (CH, major), 69.5 (CH2, major), 68.3 (CH2, minor), 60.8 (CH2,
major), 60.6 (CH2, minor), 56.0 (CH3, minor), 55.5 (CH3, major),
50.1 (CH), 33.9 (CH2, major), 27.3 (CH2, minor), 19.5 (CH3, minor),
19.5 (CH3, major), 14.6 (CH3, major), 14.6 (CH3, minor); IR (neat,
cm−1) 2975 (m), 2957 (m), 2917 (m), 2849 (m), 1732 (s), 1607 (s),
1511(s), 1296 (m), 1249 (s), 1177 (s), 1149 (s), 1091 (s), 1031 (s),
832 (m), 666 (m); HRMS (ESI) calcd for C17H22O4 + H+ 291.1591,
found 291.1590.
((7-(2-Methoxyethyl)-7,7a-dimethyltetrahydro-2H-furo[3,4-b]-
pyran-4(3H)-ylidene)methyl)triphenylstannane (49a): clear, light
yellow oil (34.9 mg, 55% yield, 1.00:0.20 dr); Rf = 0.12 (hexanes/
ethyl acetate, 2 × 9/1); 1H NMR (CDCl3, 300 MHz) δ 7.59−7.48 (m,
6H), 7.38−7.34 (m, 9H), 5.92 (s, 1H), 3.94 (t, J = 9.2 Hz, 1H), 3.87
(t, J = 8.8 Hz, 1H), 3.77 (dd, J = 11.6, 5.0 Hz, 1H), 3.58−3.53 (m,
2H), 3.48 (td, J = 12.2, 2.5 Hz, 1H), 3.35 (s, 3H), 3.15 (t, J = 9.5 Hz,
1H), 2.54 (td, J = 12.8, 6.3 Hz, 1H), 2.03 (d, J = 14.1 Hz, 1H), 1.76−
1.70 (m, 1H), 1.66−1.62 (m, 1H), 1.21 (s, 3H), 1.16 (s, 3H); 13C
NMR (CDCl3, 75 MHz) δ 154.4 (C), 138.9 (C), 137.1 (CH), 129.2
(CH), 128.9 (CH), 122.7 (CH), 87.7 (C), 84.3 (C), 69.3 (CH2), 68.4
(CH2), 62.4 (CH2), 58.9 (CH3), 56.2 (CH), 36.4 (CH2), 33.4 (CH2),
17.8 (CH3), 14.8 (CH3); IR (neat, cm−1) 3063 (m), 2931 (s), 1605
(m), 1115 (s), 1041 (s), 728 (s), 699 (s); HRMS (ESI) calcd for
C31H36O3Sn + H+ 573.1760, found 573.1754.
132.5 (CH), 131.1 (C), 128.1 (CH), 124.3 (CH), 114.8 (CH), 92.1
(CH), 68.6 (CH2), 59.5 (CH2), 55.5 (CH3), 33.0 (CH2), 19.0 (CH3),
14.8 (CH3); IR (neat, cm−1) 2980 (w), 2952 (m), 2934 (m), 2835
(w), 1709 (s), 1622 (s), 1512 (s), 1276 (s), 1249 (s), 1141 (s), 1052
(s), 967 (m), 821 (m); HRMS (ESI) calcd for C17H22O4 + H+
291.1591, found 291.1592.
Ethyl 2-(3-benzylidene-2-methyltetrahydrofuran-2-yl)acetate
(41a): clear, colorless oil (9.5 mg, 35% yield); Rf = 0.17 (hexanes/
1
dichloromethane/ethyl ether, 10/4/1); H NMR (500 MHz, CDCl3)
δ 7.37−7.30 (m, 4H), 7.25−7.20 (m, 1H), 6.23 (t, J = 2.4 Hz, 1H),
4.13 (q, J = 7.2 Hz, 2H), 4.06 (ddd, J = 8.3, 7.6, 6.0 Hz, 1H), 3.96
(ddd, J = 8.7, 7.5, 6.8 Hz, 1H), 3.01−2.86 (m, 2H), 2.70 (d, J = 19.1
Hz, 1H), 2.68 (d, J = 19.5 Hz, 1H), 1.51 (s, 3H), 1.24 (t, J = 7.2 Hz,
3H); 13C NMR (125 MHz, CDCl3) δ 170.4 (C), 147.4 (C), 137.7
(C), 128.6 (CH), 128.4 (CH), 126.9 (CH), 120.7 (CH), 83.2 (C),
65.8 (CH2), 60.5 (CH2), 45.6 (CH2), 31.8 (CH2), 26.4 (CH3), 14.5
(CH3); IR (neat, cm−1) 2979 (m), 2921 (m), 2860 (w), 1733 (s),
1448 (w), 1180 (m), 1034 (m), 695 (s); HRMS (ESI) calcd for
C16H20O3 + Na+ 283.1305, found 283.1303.
Ethyl 2-(3-(4-methoxybenzylidene)-2-methyltetrahydrofuran-2-
yl)acetate (41b): clear, colorless oil (10 mg, 33% yield); Rf = 0.33
(hexanes/dichloromethane/ether, 5/5/1); 1H NMR (500 MHz,
CDCl3) δ 7.23 (d, J = 8.7 Hz, 2H), 6.87 (d, J = 8.7 Hz, 2H), 6.15
(t, J = 2.4 Hz, 1H), 4.10 (q, J = 7.2 Hz, 2H), 4.03 (ddd, J = 8.7, 7.9, 6.0
Hz, 1H), 3.97−3.91 (m, 1H), 3.79 (s, 3H), 2.95−2.81 (m, 2H), 2.66
(d, J = 20.3 Hz, 1H), 2.64 (d, J = 20.3 Hz, 1H), 1.48 (s, 3H), 1.21 (t, J
= 7.2 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 170.5 (C), 158.6 (C),
145.0 (C), 130.5 (C), 129.6 (CH), 120.1 (CH), 114.0 (CH), 83.2
(C), 65.8 (CH2), 60.5 (CH2), 55.5 (CH3), 45.7 (CH2), 31.7 (CH2),
26.3 (CH3), 14.5 (CH3); IR (neat, cm−1) 2799 (m), 2917 (m), 1735
(s), 1608 (m), 1512 (s), 1250 (s), 1177 (m), 1033 (m), 826 (w);
HRMS (ESI) calcd for C17H22O4 + H+ 291.1591, found 291.1590.
Ethyl 4-benzylidene-2-methyltetrahydro-2H-pyran-3-carboxylate
(42a): clear, colorless oil (9.1 mg, 34% yield, 1.00/1.00 dr); Rf = 0.22
(hexanes/dichloromethane/ethyl ether, 10/4/1); 1H NMR (500
MHz, CDCl3) δ 7.37−7.30 (m, 4H), 7.27−7.20 (m, 6H), 6.49 (d, J
= 1.2 Hz, 1H), 6.46 (d, J = 1.2 Hz, 1H), 4.27 (q, J = 7.0 Hz, 2H);
4.25−4.13 (m, 3H), 4.10 (dd, J = 11.1, 6.0 Hz, 1H), 3.70 (qd, J = 6.5,
3.6 Hz, 1H), 3.59−3.52 (m, 1H), 3.54 (d, J = 3.2 Hz, 1H), 3.50 (qd, J
= 6.4, 3.4 Hz, 1H), 3.38 (ddd, J = 12.3, 11.1, 2.8 Hz, 1H), 3.24−3.12
(m, 1H), 3.17 (d, J = 3.2 Hz, 1H), 2.91 (dddd, J = 14.3, 12.3, 6.3, 2.0
((3-(((4-Methoxybut-2-en-2-yl)oxy)methyl)-2-methyldihydro-2H-
pyran-4(3H)-ylidene)methyl)triphenylstannane (50a): clear, light
yellow oil (17.4 mg, 27% yield, 1.00/0.25 dr); Rf = 0.56 (hexanes/
ethyl acetate, 2 × 4/1); 1H NMR (CDCl3, 300 MHz) δ 7.61−7.49 (m,
6H), 7.37−7.33 (m, 9H), 5.88 (s, 1H), 4.66 (t, J = 7.5 Hz, 1H), 3.99
(dd, J = 9.6, 6.5 Hz, 1H), 3.92 (dd, J = 7.5, 1.1 Hz, 2H), 3.85 (dd, J =
9.8, 7.7 Hz, 2H), 3.73 (qd, J = 6.7, 2.7 Hz, 1H), 3.31 (s, 3H), 3.31−
3.27 (m, 1H), 2.78 (td, J = 7.3, 2.4 Hz, 1H), 2.35 (tdd, J = 12.9, 5.6,
1.0 Hz, 1H), 2.04 (dt, J = 13.7, 2.6 Hz, 1H), 1.84 (s, 3H), 1.21 (d, J =
6.6 Hz, 3H); 13C NMR (CDCl3, 75 MHz) δ 158.4 (C), 158.0 (C),
139.3 (C), 137.0 (CH), 129.2 (CH), 128.8 (CH), 119.0 (CH), 93.9
(CH), 76.3 (CH), 69.1 (CH2), 68.6 (CH2), 64.2 (CH2), 57.6 (CH3),
52.8 (CH), 35.0 (CH2), 18.4 (CH3), 16.8 (CH3); IR (neat, cm−1)
3063 (s), 2932 (s), 1662 (m), 1074 (s), 1042 (s), 728 (s), 699 (s);
HRMS (ESI) calcd for C31H36O3Sn + Na+ 595.1580, found 595.1573.
8645
dx.doi.org/10.1021/jo301565u | J. Org. Chem. 2012, 77, 8634−8647