The Journal of Organic Chemistry
Article
2,3-Dihydrofuran 12 to Afford 13c and 14c. The “General
procedure for peroxycarbenium [3 + 2] cycloaddition reaction with
12” given above was used, with 3c to replace 3a. The reaction of 3c
with dihydrofuran 12 afforded 13c (a colorless oil, 44 mg, 0.19 mmol,
73% from 3c). If the experiment was done with less care in cooling
(e.g., performing the chromatography at ambient temperature),
varying amounts of the cleavage product 14c could be obtained
depending on the conditions in the individual run.
Data for cis-13c (a white solid, 10:1 PE/EtOAc Rf = 0.3): M.p. 78−
80 °C. 1H NMR (500 MHz, CDCl3) δ 7.37 (d, J = 8.5 Hz, 2H), 7.16
(d, J = 8.4 Hz, 2H), 6.05 (d, J = 5.2 Hz, 1H), 5.33 (d, J = 6.2 Hz, 1H),
4.00−3.91 (m, 2H), 3.65−3.58 (m, 1H), 1.83−1.73 (m, 1H), 1.60−
1.54 (m, 1H); 13C{1H} NMR (125 MHz, CDCl3) δ 134.2, 133.1,
129.1, 127.6, 109.1, 85.0, 69.8, 56.5, 27.2; FT-IR (KBr) 2980, 2890,
1493, 1449, 1408, 1327, 1300, 1249, 1190, 1079, 1016, 978, 959, 926,
861, 843, 772 cm−1. MS (ESI) m/z: 248.90 ([M + Na]+), 250.60 ([M
+ Na]+); HRMS (ESI) m/z: [M + Na]+ calcd. for C11H11ClNaO3
249.0289; found 249.0289.
2.33−2.25 (m, 1H), 2.25−2.19 (m, 1H), 1.83−1.73 (m, 1H), 1.60−
1.54 (m, 1H); 13C{1H} NMR (125 MHz, CDCl3) δ 139.3 (trans),
133.6, 132.0, 131.8 (trans), 127.9, 127.5 (trans), 122.3, 122.0 (trans),
109.1, 107.5 (trans), 87.7 (trans), 85.0, 69.8, 69.2 (trans), 60.8
(trans), 56.5, 32.4 (trans), 27.2; FT-IR (film of a concd solution in
CH2Cl2) 2979, 2957, 2889, 1721, 1489, 1401, 1365, 1073, 1011. 979,
958, 926, 844 cm−1. MS (ESI) m/z: 293.10 ([M + Na]+), 295.05 ([M
+ Na]+); HRMS (ESI) m/z: [M + Na]+ calcd. for C11H11BrNaO3
292.9784; found 292.9791.
Data for 14d (a white solid, less polar than trans-13d but more
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polar than cis-13d, 10:1 PE/EtOAc Rf = 0.3): M.p. 58−60 °C. H
NMR (600 MHz, CDCl3) δ 8.07 (s, 1H), 7.83 (d, J = 8.3 Hz, 2H),
7.62 (d, J = 8.2 Hz, 2H), 4.28 (t, J = 6.4 Hz, 2H), 3.06 (t, J = 7.1 Hz,
2H), 2.13 (quint, J = 6.7 Hz, 2H); 13C{1H} NMR (150 MHz, CDCl3)
δ 197.9, 161.1, 135.6, 132.1, 129.7, 128.6, 63.3, 34.8, 23.0; FT-IR
(CH2Cl2 film) 2925, 2849, 1717, 1681, 1585, 1472, 1277, 1207, 1071,
988, 827 cm−1. MS (ESI) m/z: 292.85 ([M + Na]+), 294.90 ([M +
Na]+); HRMS (ESI) m/z: [M + Na]+ calcd. For C11H11BrNaO3
292.9784; found 292.9782.
Data for a 1:1 mixture of cis-13c/trans-13c (a colorless oil, 10:1
PE/EtOAc Rf = 0.3): 1H NMR (500 MHz, CDCl3) δ 7.39−7.31 (m,
6H), 7.17−7.14 (m, 2H), 6.05 (d, J = 5.2 Hz, 1H), 5.90 (d, J = 5.0
Hz, 1H), 5.32 (d, J = 6.2 Hz, 1H), 5.11 (br s, 1H), 4.19 (ddd, J =
11.1, 8.4, 5.9 Hz, 1H), 4.08 (dt, J = 1.9, 8.1 Hz, 1H), 4.00−3.91 (m,
2H), 3.66−3.63 (m, 1H), 3.63−3.59 (m, 1H), 2.33−2.25 (m, 1H),
2.24−2.1 (m, 1H), 1.83−1.73 (m, 1H), 1.60−1.54 (m, 1H); 13C{1H}
NMR (125 MHz, CDCl3) δ 138.7 (trans), 134.1, 133.9 (trans), 133.1,
129.1, 128.9 (trans), 127.5, 127.2 (trans), 109.1, 107.4 (trans), 87.6
(trans), 85.0, 69.8, 69.2 (trans), 60.8 (trans), 56.5, 32.4 (trans), 27.2;
FT-IR (film of a concd solution in CH2Cl2) 2979, 2958, 2890, 1722,
1687, 1597, 1493, 1077, 1015, 979, 959, 926, 861, 844 cm−1. MS
(ESI) m/z: 249.15 ([M + Na]+), 251.05 ([M + Na]+); HRMS (ESI)
m/z: [M + Na]+ calcd. for C11H11ClNaO3 249.0289; found 249.0292.
Data for 14c (a white solid, less polar than trans-13c but more
(3R*,3aR*,6aS*)- and (3S*,3aR*,6aS*)-3-(p-Tolyl)tetrahydro-
3H-furo[2,3-c][1,2]dioxole (cis-13e and trans-13e) and 4-Oxo-4-
(p-tolyl)butyl Formate (14e): Reaction of 3e with 2,3-Dihydrofuran
12 to Afford 13e and 14e. The “General procedure for
peroxycarbenium [3 +2] cycloaddition reaction with 12” given
above was used, with 3e to replace 3a. The reaction of 3e with
dihydrofuran 12 afforded 13e (a colorless oil, 40 mg, 0.19 mmol, 76%
from 3e). If the experiment was done with less care in cooling (e.g.,
performing the chromatography at ambient temperature), varying
amounts of the cleavage product 14e could be obtained depending on
the conditions in the individual run.
Data for cis-13e (a white solid, 10:1 PE/EtOAc Rf = 0.3): M.p. 65−
67 °C. 1H NMR (500 MHz, CDCl3) δ 7.19 (d, J = 8.0 Hz, 1H), 7.10
(d, J = 8.1 Hz, 1H), 6.05 (d, J = 5.2 Hz, 1H), 5.33 (d, J = 6.3 Hz, 1H),
4.00 (ddd, J = 11.4, 8.2, 5.8 Hz, 1H), 3.94 (dt, J = 1.7, 8.3 Hz, 1H),
3.62−3.57 (m, 1H), 2.35 (s, 3H), 1.80−1.71 (m, 1H), 1.67−1.61 (m,
1H); 13C{1H} NMR (125 MHz, CDCl3) δ = 138.1, 131.4, 129.5,
126.2, 109.1, 85.6, 69.9, 56.6, 27.3, 21.3; FT-IR (KBr) 3002, 2971,
2921, 2885, 2859, 1515, 1488, 1447, 1347, 1327, 1307, 1275, 1247,
1187, 1072, 1016, 977, 953, 925, 863, 845, 828, 810, 760, 727 cm−1.
MS (ESI) m/z: 229.15 ([M + Na]+); HRMS (ESI) m/z: [M + Na]+
calcd. for C12H14NaO3 229.0835; found 229.0834.
Data for a 0.6:1 (because some of the cis-isomer was already
removed) mixture of cis-13e/trans-13e (a colorless oil, 10:1 PE/
EtOAc Rf = 0.3): 1H NMR (500 MHz, CDCl3) δ 7.30−7.26 (m, 2H),
7.20−7.16 (m, 3H), 7.13−7.09 (m, 2H), 6.04 (d, J = 5.2 Hz, 0.6H),
5.93 (d, J = 5.1 Hz, 1H), 5.33 (d, J = 6.2 Hz, 0.6H), 5.10 (br s, 1H),
4.20 (ddd, J = 11.1, 8.3, 5.9 Hz, 1H), 4.08 (dt, J = 2.0, 8.1 Hz, 1H),
4.00 (ddd, J = 11.4, 8.2, 5.8 Hz, 0.6H), 3.94 (dt, J = 1.7, 8.3 Hz,
0.6H), 3.72−3.67 (m, 1H), 3.62−3.56 (m, 0.6H), 2.35 (s, 1.8H), 2.34
(s, 3H), 2.30−2.24 (m, 1H), 2.23−2.18 (m, 1H), 1.81−1.71 (m,
0.6H), 1.66−1.60 (m, 0.6H); 13C{1H} NMR (125 MHz, CDCl3) δ
138.0, 137.9 (trans), 137.1 (trans), 131.4, 129.5, 129.4 (trans), 126.1,
125.8 (trans), 109.0, 107.6 (trans), 88.3 (trans), 85.6, 69.8, 69.1
(trans), 60.6 (trans), 56.6, 32.3 (trans), 27.2, 21.3, 21.2 (trans); FT-IR
(film of a concd solution in CH2Cl2) 2955, 2921, 2891, 1721, 1682,
1607, 1515, 1449, 1364, 1182, 1074, 978, 957, 925, 803 cm−1. MS
(ESI) m/z: 207.00 ([M + H]+); HRMS (ESI) m/z: [M + Na]+ calcd.
for C12H14NaO3 229.0835; found 229.0838.
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polar than cis-13c, 10:1 PE/EtOAc Rf = 0.3): M.p. 42−45 °C. H
NMR (500 MHz, CDCl3) δ 8.07 (s, 1H), 7.90 (d, J = 8.6 Hz, 2H),
7.44 (d, J = 8.6 Hz, 2H), 4.28 (t, J = 6.3 Hz, 2H), 3.06 (t, J = 7.1 Hz,
2H), 2.13 (quint, J = 6.7 Hz, 2H);13C{1H} NMR (125 MHz, CDCl3)
δ 197.7, 161.1, 139.8, 135.2, 129.5, 129.1, 63.3, 34.8, 23.1; FT-IR
(KBr) 3412, 3342, 3092, 2980, 2965, 2933, 2903, 1720, 1680, 1590,
1574, 1490, 1473, 1401, 1369, 1278, 1210.1, 1093, 1013, 989, 928,
840, 831, 807, 775, 765 cm−1. MS (ESI) m/z: 248.90 ([M + Na]+),
250.95 ([M + Na]+); HRMS (ESI) m/z: [M + Na]+ calcd. for
C11H11ClNaO3 249.0289; found 249.0295.
(3R*,3aR*,6aS*)- and (3S*,3aR*,6aS*)-3-(4-Bromophenyl)-
tetrahydro-3H-furo[2,3-c][1,2]dioxole (cis-13d and trans-13d)
and 4-(4-Bromophenyl)-4-oxobutyl Formate (14d): Reaction of
3d with 2,3-Dihydrofuran 12 to Afford 13d and 14d. The “General
procedure for peroxycarbenium [3 + 2] cycloaddition reaction with
12” given above was used, with 3d to replace 3a. The reaction of 3d
with dihydrofuran 12 afforded 13d (a colorless oil, 46 mg, 0.17 mmol,
65% from 3d). If the experiment was done with less care in cooling
(e.g., performing the chromatography at ambient temperature),
varying amounts of the cleavage product 14d could be obtained
depending on the conditions in the individual run.
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Data for cis-13d (a colorless oil, 10:1 PE/EtOAc Rf = 0.3): H
NMR (500 MHz, CDCl3) δ 7.54−7.50 (m, 2H), 7.12−7.08 (m, 2H),
6.05 (d, J = 5.2 Hz, 1H), 5.31 (d, J = 6.2 Hz, 1H), 4.00−3.92 (m,
2H), 3.65−3.58 (m, 1H), 1.83−1.73 (m, 1H), 1.60−1.54 (m, 1H);
13C{1H} NMR (125 MHz, CDCl3) δ 133.6, 132.0, 127.9, 122.3,
109.1, 85.0, 69.8, 56.5, 27.2; FT-IR (film of a concd solution in
CH2Cl2) 2980, 2890, 1493, 1449, 1408, 1327, 1300, 1249, 1190,
1079, 1016, 978, 959, 926, 861, 843, 772 cm−1. MS (ESI) m/z: 293.20
([M + Na]+), 295.10 ([M + Na]+); HRMS (ESI) m/z: [M + Na]+
calcd. for C11H11BrNaO3 292.9784; found 292.9787.
Data for a 1:1 mixture of cis-13d/trans-13d (a colorless oil, 10:1
PE/EtOAc Rf = 0.3): 1H NMR (500 MHz, CDCl3) δ 7.54−7.47 (m,
4H), 7.28−7.25 (m, 2H), 7.12−7.08 (m, 2H), 6.05 (d, J = 5.2 Hz,
1H), 5.90 (d, J = 5.0 Hz, 1H), 5.30 (d, J = 6.2 Hz, 1H), 5.09 (br s,
1H), 4.19 (ddd, J = 11.2, 8.4, 5.9 Hz, 1H), 4.08 (dt, J = 1.9, 8.1 Hz,
1H), 4.00−3.91 (m, 2H), 3.68−3.63 (m, 1H), 3.63−3.59 (m, 1H),
Data for 14e (a colorless oil, less polar than trans-13e but more
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polar than cis-13e, 10:1 PE/EtOAc Rf = 0.3): H NMR (500 MHz,
CDCl3) δ 8.07 (s, 1H), 7.88−7.86 (m, 2H), 7.28−7.25 (m, 2H), 4.28
(t, J = 6.4 Hz, 2H), 3.06 (t, J = 7.2 Hz, 2H), 2.42 (s, 3H), 2.13 (quint,
J = 6.7 Hz, 2H); 13C{1H} NMR (125 MHz, CDCl3) δ 198.7, 161.2,
144.2, 134.4, 129.5, 128.3, 63.5, 34.7, 23.2, 21.8; FT-IR (film of a
concd solution in CH2Cl2) 2958, 2920, 2843, 1723, 1681, 1606, 1574,
1404, 1363, 1178, 811 cm−1. MS (ESI) m/z: 228.95 ([M + Na]+);
HRMS (ESI) m/z: [M + Na]+ calcd. for C12H14NaO3 229.0835;
found 229.0839.
(3R*,3aR*,6aS*)- and (3S*,3aR*,6aS*)-3-(o-Tolyl)tetrahydro-
3H-furo[2,3-c][1,2]dioxole (cis-13f and trans-13f): Reaction of 3f
P
J. Org. Chem. XXXX, XXX, XXX−XXX