The Journal of Organic Chemistry
Article
200.6, 151.7, 137.4, 135.2, 133.4, 130.0, 129.3, 129.2, 127.9, 127.2,
126.9, 126.4, 125.7, 57.5, 52.9, 44.9, 41.3; endo: δ 200.6, 147.2, 136.8,
133.4, 133.0, 129.5, 129.3, 129.2, 127.5, 127.1, 126.9, 126.3, 125.2,
55.6, 51.9, 43.4, 40.1 ppm. LRMS (EI): 268 [M+], 250, 233(100), 215,
MHz, CDCl3): δ 199.8, 162.6 (d, J = 246.2 Hz), 147.4, 141.9 (d, J =
7.2 Hz), 133.5, 129.6 (d, J = 8.5 Hz), 129.4, 127.2, 126.4, 126.0, 122.5
(d, J = 2.9 Hz), 113.8 (d, J = 21.3 Hz), 112.9 (d, J = 21.2 Hz), 55.1,
53.1, 43.8, 40. 8 ppm. LRMS (EI): 252 [M+], 234, 202, 183, 170, 157,
143, 132(100), 115, 109, 101, 91, 77. IR (KBr, film) ν max: 3069, 2952,
2875, 1695, 1606, 1488, 1461, 1343, 1145, 881, 770, 747 cm−1. HRMS
(ESI): calcd for C17H13FO, [M + H]+, 253.1023; found, 253.1022.
202, 176, 151, 132, 125, 101, 89, 77, 51. IR (KBr, film) ν max: 3068,
̀
2978, 2875, 1694, 1604, 1474, 1301, 1216, 1125, 1042, 970, 886, 760,
702, 572 cm−1. HRMS (ESI): calcd for C17H13ClO, [M + H]+,
269.0728; found, 269.0743.
1
Compound exo-2f. Yellow oil; 20 mg, Yield 55%. H NMR (400
Compound 2c. Yellow oil; 33 mg, Yield 84% (mixture, exo/endo =
17:11). 1H NMR (400 MHz, CDCl3) exo: δ 8.06 (d, J = 7.2 Hz, 1H),
7.46 (dd, J = 11.9, 4.4 Hz, 2H), 7.38 (td, J = 7.5, 1.1 Hz, 1H), 7.30 (t, J
= 7.6 Hz, 2H), 7.04 (t, J = 7.4 Hz, 1H), 6.90 (d, J = 8.1 Hz, 1H), 3.88
(d, J = 5.9 Hz, 1H), 3.78 (s, 3H), 3.51−3.46 (m, 1H), 3.36 (t, J = 6.0
Hz, 1H), 3.12 (dt, J = 9.7, 5.9 Hz, 1H), 2.29 (dd, J = 9.6, 5.7 Hz, 1H);
endo: δ 7.70 (d, J = 7.5 Hz, 1H), 7.30 (t, J = 7.6 Hz, 4H), 7.18 (d, J =
7.2 Hz, 1H), 7.12 (td, J = 7.5, 1.0 Hz, 1H), 6.97 (dd, J = 11.5, 4.1 Hz,
1H), 6.77 (d, J = 7.4 Hz, 1H), 6.62 (dd, J = 17.0, 7.9 Hz, 2H), 4.36 (t,
J = 5.7 Hz, 1H), 3.90−3.83 (m, 1H), 3.73 (s, 3H), 3.69 (q, J = 5.7 Hz,
1H), 2.90 (dt, J = 9.1, 5.7 Hz, 1H), 2.36 (d, J = 9.1 Hz, 1H). 13C NMR
(100 MHz, CDCl3) exo: δ 201.6, 158.1, 152.4, 133.2, 129.4, 128.4,
128.2, 127.5, 126.9, 126.3, 125.1, 120.3, 110.3, 55.3, 53.9, 52.7, 42.9,
40.9; endo: δ 200.9, 157.4, 148.3, 132.9, 129.6, 128.4, 127.4, 127.2,
126.8, 126.2, 125.5, 119.9, 109.8, 55.4, 55.0, 53.4, 44.8, 41.7 ppm.
LRMS (EI): 264(100) [M+], 231, 202, 163, 145, 119, 91, 65, 39. IR
(KBr, film) ν max: 3068, 2946, 2836, 1694, 1603, 1461, 1350, 1180,
1028, 970, 886, 753, 574, 530 cm−1. HRMS (ESI): calcd for C18H16O2,
[M + H]+, 265.1223; found, 265.1213.
MHz, CDCl3): δ 8.06 (d, J = 7.5 Hz, 1H), 7.48 (dd, J = 10.6, 4.1 Hz,
1H), 7.39 (t, J = 7.5 Hz, 1H), 7.32 (dd, J = 8.0, 2.6 Hz, 3H), 7.23 (t, J
= 6.8 Hz, 2H), 3.79 (d, J = 6.0 Hz, 1H), 3.53 (t, J = 5.9 Hz, 1H), 3.41
(t, J = 6.1 Hz, 1H), 3.15 (dt, J = 9.8, 5.9 Hz, 1H), 2.37 (s, 3H), 2.33
(dd, J = 9.7, 6.1 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 200.2,
136.3, 135.4, 132.3, 128.4, 128.2, 126.3, 125.9, 125.9, 124.0, 57.8, 52.9,
43.2, 40.0, 20.0 ppm. LRMS (EI): 248 [M+], 233, 215, 205, 178, 156,
118, 105(100), 91, 77, 63, 51, 39. IR (KBr, film) ν max: 3024, 2948,
2921, 1697, 1605, 1514, 1460, 1381, 1297, 1015, 970, 885, 770,694
cm−1. HRMS (ESI): calcd for C18H16O, [M + H]+, 249.1274; found,
249.1275.
1
Compound endo-2f. Colorless oil; 10 mg, Yield 27%. H NMR
(400 MHz, CDCl3): δ 7.71 (dd, J = 7.6, 0.5 Hz, 1H), 7.34 (td, J = 7.4,
1.3 Hz, 1H), 7.29−7.21 (m, 1H), 7.15 (td, J = 7.5, 1.1 Hz, 1H), 6.86
(d, J = 7.9 Hz, 2H), 6.75 (d, J = 7.8 Hz, 2H), 4.43 (t, J = 5.8 Hz, 1H),
3.78 (q, J = 5.6 Hz, 1H), 3.67 (q, J = 5.7 Hz, 1H), 2.91 (dt, J = 9.2, 5.6
Hz, 1H), 2.42 (d, J = 9.2 Hz, 1H), 2.14 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ 199.4, 146.9, 135.2, 134.2, 132.3, 128.6, 127.7, 125.9, 125.5,
125.4, 124.8, 54.5, 52.2, 42.8, 40.0, 19.9 ppm. LRMS (EI): 248 [M+],
233, 215, 205, 178, 156, 118, 105(100), 91, 77, 63, 51, 39. IR (KBr,
film) ν max: 3023, 2953, 2873, 1694, 1604, 1516, 1460, 1384, 1302,
970, 885, 768,744, 704, 568 cm−1. HRMS (ESI): calcd for C18H16O,
[M + H]+, 249.1274; found, 249.1278.
Compound exo-2d. Yellow oil; 22 mg, Yield 59%. 1H NMR (400
MHz, CDCl3): δ 8.06 (d, J = 7.5 Hz, 1H), 7.49 (dd, J = 10.7, 4.0 Hz,
1H), 7.40 (t, J = 7.2 Hz, 1H), 7.31 (dd, J = 15.2, 7.5 Hz, 2H), 7.24 (s,
2H), 7.11 (d, J = 7.4 Hz, 1H), 3.79 (d, J = 6.0 Hz, 1H), 3.56 (t, J = 5.9
Hz, 1H), 3.42 (t, J = 6.1 Hz, 1H), 3.15 (dt, J = 9.8, 5.9 Hz, 1H), 2.39
(s, 3H), 2.37−2.30 (m, 1H). 13C NMR (100 MHz, CDCl3): δ 201.2,
151.9, 140.3, 138.4, 133.4, 129.3, 128.6, 127.9, 127.5, 127.4, 127.0,
125.1, 123.9, 59.0, 53.9, 44.1, 41.1, 21.6 ppm. LRMS (EI): 248(100)
[M+], 215, 187, 178, 156, 128, 105, 77, 51. IR (KBr, film) ν max: 3024,
2952, 1694, 1605, 1460, 1375, 1303, 1218, 1160, 1124, 766, 738, 701,
575 cm−1. HRMS (ESI): calcd for C18H16O, [M + H]+, 249.1274;
found, 249.1275.
Compound exo-2g. Yellow oil; 17 mg, Yield 37%. 1H NMR (400
MHz, CDCl3): δ 8.06 (d, J = 7.5 Hz, 1H), 7.54 (d, J = 8.4 Hz, 2H),
7.50 (td, J = 7.5, 1.0 Hz, 1H), 7.41 (t, J = 7.5 Hz, 1H), 7.33 (d, J = 7.6
Hz, 1H), 7.30 (d, J = 8.3 Hz, 2H), 3.76 (d, J = 6.0 Hz, 1H), 3.53 (t, J =
5.9 Hz, 1H), 3.39 (t, J = 6.1 Hz, 1H), 3.11 (dt, J = 9.9, 5.9 Hz, 1H),
2.35 (dd, J = 9.8, 6.0 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 200.6,
151.5, 139.4, 133.5, 131.8, 129.1, 128.8, 127.5, 127.1, 125.1, 120.7,
58.3, 53.7, 44.1, 40.9 ppm. LRMS (EI): 312 [M+], 271, 233, 215(100),
203, 169, 132, 102, 77, 51. IR (KBr, film) ν max: 3067, 2950, 1695,
1603, 1489, 1460, 1397, 1074, 1009, 971, 811, 777, 698, 541, 498
cm−1. HRMS (ESI): calcd for C17H13BrO, [M + H]+, 313.0223; found,
313.0219.
1
Compound endo-2d. Colorless oil; 7 mg, Yield 20%. H NMR
(400 MHz, CDCl3): δ 7.71 (d, J = 7.6 Hz, 1H), 7.34 (t, J = 7.4 Hz,
1H), 7.26−7.22 (m, 1H), 7.15 (t, J = 7.5 Hz, 1H), 6.94 (t, J = 7.6 Hz,
1H), 6.79 (d, J = 7.5 Hz, 1H), 6.69 (s, 1H), 6.65 (d, J = 7.6 Hz, 1H),
4.42 (s, 1H), 3.78 (d, J = 5.6 Hz, 1H), 3.68 (d, J = 5.7 Hz, 1H), 2.91
(d, J = 9.1 Hz, 1H), 2.42 (d, J = 9.2 Hz, 1H), 2.15 (s, 3H). 13C NMR
(100 MHz, CDCl3): δ 200.3, 147.9, 139.2, 137.6, 133.3, 129.6, 127.9,
127.4, 126.9, 126.6, 126.4, 125.8, 123.7, 55.6, 53.2, 43.8, 41.1, 21.3
ppm. LRMS (EI): 248(100) [M+], 215, 187, 178, 156, 128, 105, 77,
51. IR (KBr, film) ν max: 3024, 2952, 1694, 1605, 1460, 1375, 1303,
1218, 1160, 1124, 766, 738, 701, 575 cm−1. HRMS (ESI): calcd for
C18H16O, [M + H]+, 249.1274; found, 249.1276.
1
Compound endo-2g. Colorless oil; 14 mg, Yield 31%. H NMR
(400 MHz, CDCl3): δ 7.71 (d, J = 7.5 Hz, 1H), 7.36 (t, J = 7.4 Hz,
1H), 7.27−7.22 (m, 1H), 7.18 (dd, J = 7.3, 4.7 Hz, 3H), 6.74 (d, J =
8.1 Hz, 2H), 4.38 (t, J = 5.8 Hz, 1H), 3.78 (q, J = 5.6 Hz, 1H), 3.67 (q,
J = 5.7 Hz, 1H), 2.92 (dt, J = 9.4, 5.6 Hz, 1H), 2.43 (d, J = 9.2 Hz,
1H). 13C NMR (100 MHz, CDCl3): δ 199.8, 147.4, 138.4, 133.5,
131.2, 129.4, 128.5, 127.3, 126.4, 126.0, 119.8, 55.0, 53.0, 43.7, 40.9
ppm. LRMS (EI): 312 [M+], 271, 233, 215(100), 203, 169, 132, 102,
77, 51. IR (KBr, film) ν max: 3067, 2950, 1695, 1603, 1489, 1460, 1397,
1074, 1009, 971, 811, 777, 698, 541, 498 cm−1. HRMS (ESI): calcd for
C17H13BrO, [M + H]+, 313.0223; found, 313.0217.
Compound exo-2e. Yellow oil; 23 mg, Yield 62%. 1H NMR (400
MHz, CDCl3): δ 8.06 (d, J = 7.1 Hz, 1H), 7.50 (td, J = 7.5, 1.3 Hz,
1H), 7.44−7.32 (m, 3H), 7.20 (d, J = 7.7 Hz, 1H), 7.14 (d, J = 10.0
Hz, 1H), 7.00 (td, J = 8.5, 2.5 Hz, 1H), 3.81 (d, J = 6.0 Hz, 1H), 3.55
(t, J = 6.0 Hz, 1H), 3.41 (t, J = 6.1 Hz, 1H), 3.13 (dt, J = 9.8, 5.9 Hz,
1H), 2.36 (dd, J = 9.8, 6.0 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ
200.6, 163.2 (d, J = 246.4 Hz), 151.5, 142.9 (d, J = 7.2 Hz), 133.5,
130.3 (d, J = 8.3 Hz), 129.2, 127.5, 127.1, 125.1, 122.7 (d, J = 2.7 Hz),
114.2 (d, J = 21.7 Hz), 113.8 (d, J = 20.8 Hz), 58.5, 53.8, 44.2, 41.1
ppm. LRMS (EI): 252 [M+], 234, 202, 183, 170, 157, 143, 132(100),
115, 109, 101, 91, 77. IR (KBr, film) ν max: 3069, 2952, 2875, 1695,
1606, 1488, 1461, 1343, 1145, 881, 770, 747 cm−1. HRMS (ESI): calcd
for C17H13FO, [M + H]+, 253.1023; found, 253.1017.
Compound exo-2h. Yellow oil; 13 mg, Yield 33%. 1H NMR (400
MHz, CDCl3): δ 8.00 (d, J = 8.1 Hz, 1H), 7.44−7.38 (m, 5H), 7.36
(dd, J = 7.0, 1.9 Hz, 2H), 3.82 (d, J = 6.1 Hz, 1H), 3.53 (t, J = 5.9 Hz,
1H), 3.44 (t, J = 6.0 Hz, 1H), 3.16 (dt, J = 9.9, 5.9 Hz, 1H), 2.33 (dd, J
= 9.8, 6.1 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 199.8, 153.3,
139.8, 139.3, 128.8, 128.5, 127.7, 127.7, 127.0, 126.9, 125.4, 58.6, 53.6,
44.1, 40.6 ppm. LRMS (EI): 268 [M+], 249, 233, 215, 202, 190, 176,
162, 139, 127, 104, 101, 91(100), 77, 63, 51, 39. IR (KBr, film) ν max
:
3060, 3026, 2952, 1698, 1597, 1497, 1448, 1313, 1084, 884, 811, 736,
697, 552 cm−1. HRMS (ESI): calcd for C17H13ClO, [M + H]+,
269.0728; found, 269.0738.
1
Compound endo-2e. Colorless oil; 9 mg, Yield 24%. H NMR
(400 MHz, CDCl3): δ 7.72 (d, J = 7.6 Hz, 1H), 7.37 (td, J = 7.5, 1.3
Hz, 1H), 7.25 (d, J = 8.5 Hz, 1H), 7.18 (td, J = 7.5, 1.1 Hz, 1H), 7.03
(td, J = 7.9, 6.1 Hz, 1H), 6.71−6.63 (m, 2H), 6.59−6.52 (m, 1H), 4.42
(t, J = 5.8 Hz, 1H), 3.79 (d, J = 5.6 Hz, 1H), 3.68 (d, J = 5.7 Hz, 1H),
2.93 (dt, J = 9.2, 5.6 Hz, 1H), 2.44 (d, J = 9.2 Hz, 1H). 13C NMR (100
Compound endo-2h. Colorless solid (mp 119.6−122.5 °C); 11
1
mg, Yield 29%. H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.2 Hz,
1H), 7.25 (d, J = 1.9 Hz, 1H), 7.15−7.06 (m, 3H), 7.01 (t, J = 7.3 Hz,
1H), 6.86 (d, J = 7.8 Hz, 2H), 4.47 (t, J = 5.8 Hz, 1H), 3.78 (q, J = 5.6
Hz, 1H), 3.69 (q, J = 5.7 Hz, 1H), 2.93 (dt, J = 9.4, 5.6 Hz, 1H), 2.41
J
dx.doi.org/10.1021/jo5013465 | J. Org. Chem. XXXX, XXX, XXX−XXX