Paper
Organic & Biomolecular Chemistry
(m, 1 H), 4.59 (d, J = 6.8, 1 H), 1.67–1.61 (m, 1 H); 13C NMR 1343, 1223, 1183, 1126, 1110, 1080, 1052, 1016, 946, 909, 854,
(100 MHz, CDCl3): δ 148.96, 147.15, 145.43, 136.92, 130.81, 815, 784, 749, 710, 695, 666, 627 cm−1; MS(EI) m/z (%): 347
130.18, 128.67, 127.78, 125.03, 123.37, 122.68, 119.08, 116.36, (M+, 26), 59 (100); HRMS: calcd for C21H17NO4 (M+), 347.1158;
70.61, 43.13; IR (neat): 3433, 2918, 1703, 1595, 1513, 1492, found, 347.1164.
1445, 1344, 1222, 1182, 1129, 1109, 1071, 1050, 946, 908, 854,
(4) Preparation of (4R*,5R*)-3-(4-methoxyphenyl)-4-(4-
814, 786, 767, 731, 692, 664, 621 cm−1; MS(EI) m/z (%): 333 nitrophenyl)-4,5-dihydroisobenzo-furan-5-ol (3ad) and (4R*,5S*)-
(M+, 3), 84 (100); HRMS: calcd for C20H15NO4 (M+), 333.1001; 3-(4-methoxyphenyl)-4-(4-nitrophenyl)-4,5-dihydroisobenzo-
found, 333.1002.
furan-5-ol (3ad′). The reaction of PdCl2(PPh3)2 (9 mg, 5 mol%),
(2) Preparation of (4R*,5R*)-3-(4-bromophenyl)-4-(4-nitro- CuI (2 mg, 4 mol%), 1a (62 mg, 0.25 mmol) and 2d (73 mg,
phenyl)-4,5-dihydroisobenzofuran-5-ol (3ab) and (4R*,5S*)-3- 0.3 mmol) in 1 mL of toluene and 0.6 mL of i-Pr2NH afforded
(4-bromophenyl)-4-(4-nitrophenyl)-4,5-dihydroisobenzofuran- 3ad (50 mg, 55%) and 3ad′ (4 mg, 4%) (eluent: petroleum
5-ol (3ab′). The reaction of PdCl2(PPh3)2 (9 mg, 5 mol%), CuI ether–ethyl acetate = 4/1) as a liquid:
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(2 mg, 4 mol%), 1a (62 mg, 0.25 mmol) and 2b (87 mg,
3ad H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 8.0 Hz, 2 H),
0.3 mmol) in 1 mL of toluene and 0.6 mL of i-Pr2NH afforded 7.52 (s, 1 H), 7.29 (d, J = 7.6 Hz, 2 H), 6.80 (d, J = 8.4 Hz, 2 H),
3ab (62 mg, 60%) (eluent: petroleum ether–ethyl acetate = 4/1) 6.72 (d, J = 10.0 Hz, 1 H), 5.88 (dd, J1 = 9.2 Hz, J2 = 5.2 Hz,
as a liquid; 3ab′ was contaminated with some unknown impu- 1 H), 4.59 (s, 1 H), 4.31 (d, J = 3.6, 1 H), 3.74, (s, 3 H), 2.43 (s,
rities and thus not characterized.
3ab H NMR (400 MHz, CDCl3): δ 8.11 (d, J = 8.4 Hz, 2 H), 146.67, 136.65, 128.78, 126.27, 125.50, 123.79, 122.94, 121.96,
7.60 (s, 1 H), 7.42 (d, J = 8.4 Hz, 2 H), 7.32 (d, J = 8.8, 2 H), 121.61, 113.97, 112.35, 70.59, 55.11, 45.49; IR (neat): 3417,
1 H); 13C NMR (100 MHz, CDCl3): δ 158.98, 150.34, 148.01,
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7.26–7.24 (m, 2 H), 6.77 (d, J = 10.0 Hz, 1 H), 5.96 (dd, J1
=
2908, 1600, 1510, 1461, 1346, 1301, 1250, 1178, 1111, 1060,
9.6 Hz, J2 = 5.2 Hz, 1 H), 4.62 (d, J = 1.2 Hz, 1 H), 4.37 (dd, J1 = 1026, 954, 904, 831, 790, 733, 699, 622 cm−1; MS(EI) m/z (%):
5.6 Hz, J2 = 2.0 Hz, 1 H), 1.87 (brs, 1 H); 13C NMR (100 MHz, 363 (M+, 60), 135 (100), 84 (98); HRMS: calcd for C21H17NO5
CDCl3): δ 149.48, 147.41, 147.02, 137.65, 131.84, 129.02, (M+), 363.1107; found, 363.1104.
128.83, 126.35, 125.88, 124.03, 121.98, 121.90, 121.78, 114.76,
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3ad′ H NMR (400 MHz, CDCl3): δ 8.13 (d, J = 8.4 Hz, 2 H),
70.65, 45.63; IR (neat): 3433, 2918, 1595, 1513, 1492, 1445, 7.47 (s, 1 H), 7.41 (d, J = 8.4 Hz, 2 H), 7.29 (d, J = 8.8 Hz, 2 H),
1344, 1222, 1182, 1129, 1109, 1071, 1050, 946, 908, 854, 814, 6.84 (d, J = 8.8 Hz, 2 H), 6.56 (dd, J1 = 10.4 Hz, J2 = 2.8 Hz,
786, 767, 731, 692, 664, 621 cm−1; MS(EI) m/z (%): 413 1 H), 5.60 (dd, J1 = 9.6 Hz, J2 = 1.6 Hz, 1 H), 4.96 (m, 1 H), 4.55
[M+(81Br), 4], 411 [M+(79Br), 4], 57 (100); HRMS: calcd for (d, J = 7.2 Hz, 1 H), 3.78 (s, 3 H), 1.59 (brs, 1 H); 13C NMR
C20H14NO4Br [M+(79Br)], 411.0106; found, 411.0107.
(100 MHz, CDCl3): δ 159.23, 149.07, 147.13, 145.71, 136.35,
(3) Preparation of (4R*,5R*)-4-(4-nitrophenyl)-3-p-tolyl-4,5- 130.78, 130.56, 126.49, 123.36, 123.08, 122.56, 119.21, 114.72,
dihydroisobenzofuran-5-ol (3ac) and (4R*,5S*)-4-(4-nitrophe- 114.14, 70.51, 55.27, 43.09; IR (neat): 3398, 2920, 1702, 1602,
nyl)-3-p-tolyl-4,5-dihydroisobenzofuran-5-ol (3ac′). The reac- 1513, 1343, 1223, 1183, 1126, 1110, 1080, 1052, 1016, 946, 909,
tion of PdCl2(PPh3)2 (9 mg, 5 mol%), CuI (1 mg, 3 mol%), 1a 854, 815, 784, 749, 710, 695, 666, 627 cm−1; MS(EI) m/z (%):
(62 mg, 0.25 mmol) and 2c (68 mg, 0.3 mmol) in 1 mL of 363 (M+, 44), 84 (100); HRMS: calcd for C21H17NO5 (M+),
toluene and 0.6 mL of i-Pr2NH afforded 3ac (58 mg, 67%) and 363.1107; found, 363.1111.
3ac′ (4 mg, 5%) (eluent: petroleum ether–ethyl acetate = 4/1) as
(5) Preparation of (4R*,5R*)-4-(2-nitrophenyl)-3-phenyl-4,5-
dihydroisobenzofuran-5-ol (3ba) and (4R*,5S*)-4-(2-nitrophe-
a liquid:
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3ac H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 8.4 Hz, 2 H), nyl)-3-phenyl-4,5-dihydroisobenzofuran-5-ol (3ba′). The reac-
7.56 (s, 1 H), 7.33–7.25 (m, 4 H), 7.09 (d, J = 8.0 Hz, 2 H), 6.75 tion of PdCl2(PPh3)2 (9 mg, 5 mol%), CuI (1 mg, 3 mol%), 1b
(d, J = 9.2 Hz, 1 H), 5.93 (dd, J1 = 9.6 Hz, J2 = 5.6 Hz, 1 H), 4.64 (62 mg, 0.25 mmol) and 2a (64 mg, 0.3 mmol) in 1 mL of
(d, J = 1.2 Hz, 1 H), 4.34 (dd, J1 = 5.6 Hz, J2 = 2.0 Hz, 1 H), 2.29 toluene and 0.6 mL of i-Pr2NH afforded 3ba (44 mg, 53%) and
(s, 3 H), 2.03 (brs, 1 H); 13C NMR (100 MHz, CDCl3): δ 150.69, 3ba′ (12 mg, 14%) (eluent: petroleum ether–ethyl acetate = 4/1)
147.95, 146.84, 137.71, 137.02, 129.30, 128.85, 127.39, 125.65, as a liquid:
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124.87, 123.87, 122.06, 121.69, 113.27, 70.70, 45.65, 21.15; IR
3ba H NMR (400 MHz, CDCl3): δ 7.90 (dd, J1 = 8.0 Hz, J2 =
(neat): 3391, 2876, 1597, 1514, 1491, 1444, 1390, 1344, 1108, 2.0 Hz, 1 H), 7.57 (s, 1 H), 7.37–7.31 (m, 4 H), 7.26 (t, J = 8.0 Hz,
1053, 1006, 952, 902, 836, 791, 766, 690, 631 cm−1; MS(EI) m/z 2 H), 7.20–7.16 (m, 1 H), 7.05–7.02 (m, 1 H), 6.78 (d, J = 9.6 Hz,
(%): 347 (M+, 96), 119 (100), 84 (83); HRMS: calcd for 1 H), 5.93 (dd, J1 = 10.0 Hz, J2 = 5.6 Hz, 1 H), 5.11 (d, J = 2.0 Hz,
C21H17NO4 (M+), 347.1158; found, 347.1151.
1 H), 4.49 (d, J = 4.0 Hz, 1 H), 2.22 (brs, 1 H); 13C NMR
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3ac′ H NMR (400 MHz, CDCl3): δ 8.13 (d, J = 8.0 Hz, 2 H), (100 MHz, CDCl3): δ 149.96, 149.34, 137.05, 134.65, 133.00,
7.49 (s, 1 H), 7.41 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 6.8, 2 H), 7.11 130.20, 130.06, 128.54, 127.92, 127.56, 125.95, 124.79, 124.55,
(d, J = 7.6 Hz, 2 H), 6.57 (dd, J1 = 10.4 Hz, J2 = 1.6 Hz, 1 H), 122.37, 121.66, 114.64, 69.76, 40.90; IR (neat): 3401, 2922, 1600,
5.60 (d, J = 10.0 Hz, 1 H), 4.97 (d, J = 5.6 Hz, 1 H), 4.58 (d, J = 1522, 1492, 1444, 1350, 1261, 1127, 1004, 952, 908, 855, 766,
7.6 Hz, 1 H), 2.31 (s, 3 H), 1.57 (brs, 1 H); 13C NMR (100 MHz, 734, 691, 641, 614 cm−1; MS(EI) m/z (%): 333 (M+, 13), 105 (100);
CDCl3): δ 149.23, 147.18, 145.55, 137.80, 136.62, 130.80, HRMS: calcd for C20H15NO4 (M+), 333.1001; found, 333.1008.
130.68, 129.38, 127.46, 124.98, 123.38, 122.61, 119.19, 115.62,
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3ba′ H NMR (400 MHz, CDCl3): δ 7.84–7.82 (m, 1 H), 7.50
70.65, 43.16, 21.20; IR (neat): 3398, 2920, 1702, 1602, 1513, (s, 1 H), 7.44–7.40 (m, 3 H), 7.37–7.29 (m, 3 H), 7.35–7.19 (m,
5958 | Org. Biomol. Chem., 2013, 11, 5954–5962
This journal is © The Royal Society of Chemistry 2013