PAPER
Mo(CO)6-Mediated Alkoxycarbonylation of Aryl Halides
2307
1H NMR (400 MHz, CDCl3): d = 5.47 (s, 2 H), 7.37–7.62 (m, 7 H),
7.89 (d, J = 8.8 Hz, 2 H), 7.96 (d, J = 8.0 Hz, 1 H), 8.13 (d, J = 8.4
Hz, 1 H), 8.68 (s, 1 H).
13C NMR (100 MHz, CDCl3): d = 66.8, 125.2, 126.6, 127.3, 127.7,
128.1, 128.2, 128.22, 128.6, 129.3, 131.2, 132.4, 135.5, 136.1,
166.5.
Naphthalene-2-carboxylic Acid (3an)12
Yield: 39 mg (45%); white solid.
1H NMR (400 MHz, CDCl3): d = 7.56–7.65 (m, 2 H), 7.92 (m, 2 H),
8.00 (d, J = 8.4 Hz, 1 H), 8.14 (dd, J = 1.6, 8.4 Hz, 1 H), 8.74 (s, 1
H).
13C NMR (75 MHz, CDCl3): d = 125.4, 126.5, 126.8, 127.8, 128.3,
128.7, 129.5, 132.2, 132.4, 135.9, 172.2.
2-(4-Methoxyphenyl)ethyl Naphthalene-2-carboxylate (3aj)
Yield: 74 mg (48%); white solid; mp 95–97 °C (EtOAc).
Phenyl Naphthalene-1-carboxylate (3ba)13
IR (NaCl, CH2Cl2): 3055, 1714, 1631, 1514, 1265, 1228, 1195,
1130, 1095, 736, 704 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.06 (t, J = 7.2 Hz, 2 H), 3.77 (s,
3 H), 4.54 (t, J = 7.2 Hz, 2 H), 6.86 (d, J = 8.4 Hz, 2 H), 7.22 (d,
J = 8.4 Hz, 2 H), 7.50–7.58 (m, 2 H), 7.85 (d, J = 8.4 Hz, 2 H), 7.92
(d, J = 8.0 Hz, 1 H), 8.03 (d, J = 8.4 Hz, 1 H), 8.57 (s, 1 H).
13C NMR (100 MHz, CDCl3): d = 34.4, 55.2, 65.8, 113.9, 125.2,
126.6, 127.5, 127.7, 128.1, 128.2, 129.3, 129.85, 129.91, 131.0,
132.4, 135.5, 158.3, 166.6.
Yield: 101 mg (81%); white solid.
1H NMR (300 MHz, CDCl3): d = 7.35–7.73 (m, 8 H), 7.96 (d,
J = 8.4 Hz, 1 H), 8.13 (d, J = 8.1 Hz, 1 H), 8.53 (dd, J = 1.2, 7.5 Hz,
1 H), 9.13 (d, J = 8.7 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 121.8, 124.4, 125.7, 125.8, 125.9,
126.3, 128.1, 128.6, 129.5, 131.1, 131.6, 133.8, 134.2, 150.9, 165.7.
Phenyl Benzoate (3ca)3g
Yield: 88 mg (89%); white solid.
HRMS (ESI): m/z [M + H]+ calcd for C20H19O3: 307.1334; found:
307.1337.
1H NMR (400 MHz, CDCl3): d = 7.20–7.27 (m, 3 H), 7.42 (t, J = 8.0
Hz, 2 H), 7.49 (t, J = 8.0 Hz, 2 H), 7.61 (t, J = 7.6 Hz, 1 H), 8.20 (d,
J = 7.6 Hz, 2 H).
2-Methylpropyl Naphthalene-2-carboxylate (3ak)
Yield: 58 mg (51%); colorless oil.
13C NMR (100 MHz, CDCl3): d = 121.7, 125.8, 128.5, 129.4, 129.5,
130.1, 133.5, 150.9, 165.1.
IR (NaCl, CH2Cl2): 3059, 2962, 1712, 1631, 1469, 1375, 1276,
1226, 1195, 1130, 1095, 989, 866, 825, 779, 761 cm–1.
Phenyl 2-Methoxybenzoate (3da)14
Yield: 86 mg (75%); pale-yellow solid.
1H NMR (400 MHz, CDCl3): d = 3.91 (s, 3 H), 7.00–7.05 (m, 2 H),
7.20–7.25 (m, 3 H), 7.38–7.54 (m, 3 H), 8.01 (d, J = 7.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 55.9, 112.1, 119.0 120.1, 121.8,
125.6, 129.3, 132.1, 134.2, 150.9, 159.8, 164.3.
1H NMR (300 MHz, CDCl3): d = 1.09 (d, J = 6.6 Hz, 6 H), 2.17
(hept, J = 6.6 Hz, 1 H), 4.20 (d, J = 6.6 Hz, 2 H), 7.54–7.64 (m, 2
H), 7.91 (d, J = 8.4 Hz, 2 H), 7.99 (d, J = 7.8 Hz, 1 H), 8.10 (dd,
J = 1.5, 8.6 Hz, 1 H), 8.64 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 19.2, 28.0, 71.1, 125.2, 126.6,
127.7, 127.8, 128.08, 128.13, 129.3, 130.9, 132.5, 135.5, 166.8.
Phenyl 3-Methoxybenzoate (3ea)15
Yield: 86 mg (75%); white solid.
1H NMR (400 MHz, CDCl3): d = 3.85 (s, 3 H), 7.15–7.28 (m, 4 H),
7.41 (q, J = 8.0 Hz, 3 H), 7.70 (m, 1 H), 7.80 (d, J = 8.0 Hz, 1 H).
HRMS (ESI): m/z [M + H]+ calcd for C15H17O2: 229.1229; found:
229.1235.
Pentyl Naphthalene-2-carboxylate (3al)11
Yield: 68 mg (56%); colorless oil.
13C NMR (100 MHz, CDCl3): d = 55.4, 114.4, 120.1, 121.6, 122.5,
IR (NaCl, CH2Cl2): 3059, 2956, 2870, 1712, 1631, 1467, 1354,
1278, 1228, 1195, 1130, 1095, 970, 866, 779, 738, 704 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.97 (t, J = 7.2 Hz, 3 H), 1.40–1.51
(m, 4 H), 1.77–1.88 (m, 2 H), 4.40 (t, J = 6.6 Hz, 2 H), 7.51–7.61
(m, 2 H), 7.87 (d, J = 8.7 Hz, 2 H), 7.96 (d, J = 8.1 Hz, 1 H), 8.10
(dd, J = 1.5, 8.6 Hz, 1 H), 8.63 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 13.9, 22.3, 28.2, 28.4, 65.2, 125.2,
126.5, 127.67, 127.73, 128.0, 128.1, 129.3, 130.9, 132.5, 135.4,
166.8.
125.8, 129.4, 129.5, 130.8, 150.9, 159.6, 165.0.
Phenyl 4-Methoxybenzoate (3fa)16
Yield: 99 mg (87%); white solid.
1H NMR (400 MHz, CDCl3): d = 3.86 (s, 3 H), 6.96 (d, J = 9.2 Hz,
2 H), 7.19–7.26 (m, 3 H), 7.41 (t, J = 8.0 Hz, 2 H), 8.14 (d, J = 9.2
Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 55.4, 113.8, 121.7, 121.8, 125.6,
129.4, 132.2, 151.0, 163.8, 164.8.
HRMS (ESI): m/z [M + H]+ calcd for C16H19O2: 243.1385; found:
243.1387.
Ethyl Phenyl Terephthalate (3ga)
Yield: 84 mg (62%); white solid; mp 99–101 °C (EtOAc).
Cyclopentyl Naphthalene-2-carboxylate (3am)
Yield: 63 mg (52%); colorless oil.
IR (NaCl, CH2Cl2): 3055, 1737, 1716, 1635, 1490, 1408, 1265,
1195, 1107, 1076, 1018, 736, 705 cm–1.
IR (NaCl, CH2Cl2): 3059, 2964, 2827, 1708, 1631, 1465, 1352,
1284, 1228, 1197, 1130, 1097, 962, 866, 779, 761, 736, 704 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.64–2.06 (m, 8 H), 5.46–5.49 (m,
1 H), 7.52–7.60 (m, 2 H), 7.87 (d, J = 8.4 Hz, 2 H), 7.96 (d, J = 8.0
Hz, 1 H), 8.05 (d, J = 8.8 Hz, 1 H), 8.57 (s, 1 H).
1H NMR (300 MHz, CDCl3): d = 1.45 (t, J = 7.2 Hz, 3 H), 4.45 (q,
J = 7.2 Hz, 2 H), 7.24–7.33 (m, 3 H), 7.46 (t, J = 7.8 Hz, 2 H), 8.19
(d, J = 8.4 Hz, 2 H), 8.28 (d, J = 8.4 Hz, 2 H).
13C NMR (75 MHz, CDCl3): d = 14.2, 61.5, 121.5, 126.0, 129.5,
129.6, 130.0, 133.2, 134.8, 150.7, 164.3, 165.6.
13C NMR (100 MHz, CDCl3): d = 23.9, 32.8, 77.8, 125.3, 126.5,
127.7, 128.0, 128.07, 128.13, 129.3, 130.8, 132.5, 135.4, 166.5.
HRMS (ESI): m/z [M + H]+ calcd for C16H15O4: 271.0970; found:
271.0974.
HRMS (ESI): m/z [M + H]+ calcd for C16H17O2: 241.1229; found:
241.1229.
Phenyl Thiophene-3-carboxylate (3ha)16
Yield: 91 mg (89%); white solid; mp 59–61 °C (EtOAc).
Synthesis 2011, No. 14, 2303–2309 © Thieme Stuttgart · New York