10.1002/ejoc.201701622
European Journal of Organic Chemistry
FULL PAPER
liquid. [TLC control (petroleum ether/ethyl acetate 95:5), Rf(2g)=0.40,
Rf(4gg)=0.85, UV detection]. IR (MIR-ATR, 4000–600 cm-1): max=2927,
1665, 1586, 1481, 1328, 1258, 1197, 825 cm-1.1H NMR (CDCl3, 400 MHz):
δ=7.53 (d, 2H, J=8.3 Hz, ArH), 7.33 (d, 2H, J=8.3 Hz, ArH), 7.14 (s, 1H,
ArH), 7.13 (s, 1H, ArH), 6.44 (t, 1H, J=1.9 Hz, C=CH), 3.93 (s, 3H, ArOCH3),
3.90 (s, 3H, ArOCH3), 3.43 (d, 2H, J=1.9 Hz, CH2), 2.97 [sept, 1H, J=6.8
Hz, CH(CH3)2], 1.31 [d, 6H, J=6.8 Hz, CH(CH3)2] ppm. 13C NMR (CDCl3,
100 MHz): δ=148.2 (s, Cq), 148.0 (s, Cq), 147.3 (s, Cq), 144.8 (s, Cq), 137.2
(s, Cq), 136.7 (s, Cq), 133.8 (s, Cq), 129.1 (d, C=CH), 127.4 (d, 2C, 2 ×
ArCH), 126.7 (d, 2C, 2 × ArCH), 108.1 (d, ArCH), 104.1 (d, ArCH), 56.2 (q,
2C, 2 × ArOCH3), 38.0 (t, CH2), 33.9 [d, CH(CH3)2], 24.0 [q, 2C, CH(CH3)2]
ppm. HR-MS (ESI+) m/z calculated for [C20H23O2]+=[M+H]+: 295.1698;
found 295.1699.
(1.0 mL) for ketone 3ag at 80 C for 24 h, and then with TfOH (0.44 mL,
5 mmol) for indene at 80C for 24 h. Purification of the crude material by
silica gel column chromatography (petroleum ether/ethyl acetate 100:0 to
99:1) furnished the indene 4ag (86.6 mg, 74%) as colour less viscous
liquid. [TLC control (petroleum ether/ethyl acetate 100:0), Rf(2g)=0.10,
Rf(4ag)=0.85, UV detection]. IR (MIR-ATR, 4000–600 cm-1): max=3031,
2858, 1643, 1468, 1377, 1261, 1058, 821, 758 cm-1. 1H NMR (CDCl3, 400
MHz): δ=7.61 (d, 1H, J=7.8 Hz, ArH), 7.57–7.47 (m, 1H, ArH), 7.54 (d, 2H,
J=7.8 Hz, ArH), 7.38–7.28 (m, 1H, ArH), 7.31 (d, 2H, J=7.8 Hz, ArH), 7.24
(ddd, 1H, J=7.8, 7.3 and 1.0 Hz, ArH), 6.59 (t, 1H, J=2.4 Hz, C=CH), 3.49
(d, 2H, J=2.4 Hz, CH2), 2.97 [sept, 1H, J=7.3 Hz, CH(CH3)2], 1.30 [d, 6H,
J=7.3 Hz, CH(CH3)2] ppm. 13C NMR (CDCl3, 100 MHz): δ=148.2 (s, Cq),
145.0 (s, Cq), 144.8 (s, Cq), 144.0 (s, Cq), 133.6 (s, Cq), 130.4 (d, ArCH),
127.6 (d, 2C, 2 × ArCH), 126.6 (d, 2C, 2 × ArCH), 126.1 (d, ArCH), 124.7
(d, ArCH), 124.0 (d, ArCH), 120.4 (d, C=CH), 38.1 (t, CH2), 33.9 [d,
CH(CH3)2], 24.0 [q, 2C, CH(CH3)2] ppm. HR-MS (ESI+) m/z calculated for
[C18H19]+=[M+H]+: 235.1487; found 235.1487.
3-(4-Fluorophenyl)-5,6-dimethoxy-1H-indene (4gi): GP-1 was carried
out with alcohol 2i (76 mg, 0.5 mmol), iodoarene 1g (158.4 mg, 0.5 mmol),
Pd(OAc)2 (3.4 mg, 3 mol%), triethylamine (0.2 mL, 1.5 mmol), and DCE
(1.0 mL) for ketone 3gi at 80 C for 24 h, and then with TfOH (0.44 mL, 5
mmol) for indene at rt for 6 h. Purification of the crude material by silica gel
column chromatography (petroleum ether/ethyl acetate 100:0 to 95:5)
furnished the indene 4gi (106.6 mg, 79%) as colour less viscous liquid.
[TLC control (petroleum ether/ethyl acetate 95:5), Rf(2i)=0.40,
Rf(4gi)=0.75, UV detection]. IR (MIR-ATR, 4000–600 cm-1): max=3032,
2893, 1647, 1548, 1455, 1400, 1254, 760 cm-1.1H NMR (CDCl3, 400 MHz):
δ=7.53 (dd, 2H, J=8.8 and 5.3 Hz, ArH), 7.15 (d, 2H, J=8.8 Hz, ArH), 7.13
(s, 1H, ArH), 7.04 (s, 1H, ArH), 6.42 (t, 1H, J=2.0 Hz, C=CH), 3.93 (s, 3H,
ArOCH3), 3.88 (s, 3H, ArOCH3), 3.43 (d, 2H, J=2.0 Hz, CH2) ppm. 13C NMR
(CDCl3, 100 MHz): δ=162.2 (d, J=246.5 Hz, Cq), 148.1 (s, Cq), 147.5 (s,
Cq), 143.9 (s, Cq), 137.1 (s, Cq), 136.5 (s, Cq), 132.3 (d, J=3.7 Hz, Cq),
129.5 (d, C=CH), 129.0 (d, 2C, J=8.1 Hz, 2 × ArCH), 115.5 (d, 2C, J=21.3
Hz, 2 × ArCH), 108.1 (d, ArCH), 103.8 (d, ArCH), 56.2 (q, 2C, 2 × ArOCH3),
38.0 (t, CH2) ppm. HR-MS (ESI+) m/z calculated for [C17H16FO2]+=[M+H]+:
271.1134; found: 271.1133.
3-(2-Ethylphenyl)-5,6-dimethoxy-1H-indene (4gb): GP-1 was carried
out with alcohol 2b (81 mg, 0.5 mmol), iodoarene 1g (158.4 mg, 0.5 mmol),
Pd(OAc)2 (3.4 mg, 3 mol%), triethylamine (0.2 mL, 1.5 mmol), and DCE
(1.0 mL) for ketone 3gb at 80 C for 24 h, and then with TfOH (0.44 mL,
5 mmol) for indene at rt for 6 h. Purification of the crude material by silica
gel column chromatography (petroleum ether/ethyl acetate 100:0 to 95:5)
furnished the indene 4gb (68.6 mg, 49%) as colour less viscous liquid.
[TLC control (petroleum ether/ethyl acetate 95:5), Rf(2b)=0.40,
Rf(4gb)=0.85, UV detection]. IR (MIR-ATR, 4000–600 cm-1): max= 2906,
1650, 1561, 1328, 1104, 830, 786 cm-1. 1H NMR (CDCl3, 400 MHz):
δ=7.40–7.30 (m, 2H, ArH), 7.27–7.20 (m, 2H, ArH), 7.13 (s, 1H, ArH), 6.63
(s, 1H, ArH), 6.32 (t, 1H, J=2.0 Hz, C=CH), 3.92 (s, 3H, ArOCH3), 3.79 (s,
3H, ArOCH3), 3.47 (d, 2H, J=2.0 Hz, CH2), 2.61 (q, 2H, J=7.3 Hz, CH2CH3),
1.12 (t, 3H, J=7.3 Hz, CH2CH3) ppm. 13C NMR (CDCl3, 100 MHz): δ=148.2
(s, Cq), 147.2 (s, Cq), 144.5 (s, Cq), 142.6 (s, Cq), 138.5 (s, Cq), 136.1 (s,
Cq), 135.3 (s, Cq), 130.1 (d, ArCH), 129.6 (d, ArCH), 128.5 (d, ArCH), 127.7
(d, ArCH), 125.6 (d, C=CH), 107.9 (d, ArCH), 103.9 (d, ArCH), 56.2 (q,
ArOCH3), 56.1 (q, ArOCH3), 38.2 (t, CH2), 26.3 (t, CH2CH3), 15.8 (q,
CH2CH3) ppm. HR-MS (ESI+) m/z calculated for [C19H21O2]+=[M+H]+:
281.1542; found: 281.1540.
3-(4-Chlorophenyl)-5,6-dimethoxy-1H-indene (4gj): GP-1 was carried
out with alcohol 2j (84 mg, 0.5 mmol), iodoarene 1g (158.4 mg, 0.5 mmol),
Pd(OAc)2 (3.4 mg, 3 mol%), triethylamine (0.2 mL, 1.5 mmol), and DCE
(1.0 mL) for ketone 3gj at 80 C for 24 h, and then with TfOH (0.44 mL, 5
mmol) for indene at rt for 6 h. Purification of the crude material by silica gel
column chromatography (petroleum ether/ethyl acetate 100:0 to 95:5)
furnished the indene 4gj (100.3 mg, 70%) as colour less semisolid. [TLC
control (petroleum ether/ethyl acetate 95:5), Rf(2j)=0.45, Rf(4gj)=0.80, UV
detection]. IR (MIR-ATR, 4000–600 cm-1): max=3034, 2896, 1696, 1578,
1462, 1267, 1029, 866, 747 cm-1. 1H NMR (CDCl3, 400 MHz): δ=7.50 (d,
2H, J=8.3 Hz, ArH), 7.42 (d, 2H, J=8.3 Hz, ArH), 7.12 (s, 1H, ArH), 7.03
(s, 1H, ArH), 6.45 (t, 1H, J=2.0 Hz, C=CH), 3.92 (s, 3H, ArOCH3), 3.88 (s,
3H, ArOCH3), 3.43 (d, 2H, J=2.0 Hz, CH2) ppm. 13C NMR (CDCl3, 100
MHz): δ=148.1 (s, Cq), 147.5 (s, Cq), 143.8 (s, Cq), 137.1 (s, Cq), 136.3 (s,
Cq), 134.8 (s, Cq), 133.2 (s, Cq), 129.9 (d, C=CH), 128.8 (d, 4C, 4 × ArCH),
108.2 (d, ArCH), 103.8 (d, ArCH), 56.2 (q, 2C, 2 × ArOCH3), 38.1 (t, CH2)
ppm. HR-MS (ESI+) m/z calculated for [C17H16ClO2]+=[M+H]+: 287.0839;
found: 287.0840.
3-(3-Methoxyphenyl)-5,6-dimethoxy-1H-indene (4gc): GP-1 was
carried out with alcohol 2c (82 mg, 0.5 mmol), iodoarene 1g (158.4 mg,
0.5 mmol), Pd(OAc)2 (3.4 mg, 3 mol%), triethylamine (0.2 mL, 1.5 mmol),
and DCE (1.0 mL) for ketone 3gc at 80 C for 24 h, and then with TfOH
(0.44 mL, 5 mmol) for indene at rt for 6 h. Purification of the crude material
by silica gel column chromatography (petroleum ether/ethyl acetate 100:0
to 93:7) furnished the indene 4gc (97.4 mg, 69%) as colour less semisolid.
[TLC control (petroleum ether/ethyl acetate 93:7), Rf(2c)=0.35,
Rf(4gc)=0.75, UV detection]. IR (MIR-ATR, 4000–600 cm-1): max=2967,
1639, 1584, 1477, 1329, 1262, 1198, 843 cm-1.1H NMR (CDCl3, 400 MHz):
δ=7.38 (dd, 1H, J=8.3 and 7.8 Hz, ArH), 7.22–7.05 (m, 4H, ArH), 6.93 (dd,
1H, J=8.3, 2.4 and 1.0 Hz, ArH), 6.47 (t, 1H, J=2.0 Hz, C=CH), 3.93 (s, 3H,
ArOCH3), 3.88 (s, 3H, ArOCH3), 3.86 (s, 3H, ArOCH3), 3.44 (d, 2H, J=2.0
Hz, CH2) ppm. 13C NMR (CDCl3, 100 MHz): δ=159.8 (s, Cq), 148.0 (s, Cq),
147.4 (s, Cq), 144.8 (s, Cq), 137.7 (s, Cq), 137.1 (s, Cq), 136.5 (s, Cq), 129.7
(d, C=CH), 119.9 (d, ArCH), 113.1 (d, ArCH), 108.1 (d, ArCH), 104.0 (d,
ArCH), 56.2 (q, 2C, 2 × ArOCH3), 55.2 (q, ArOCH3), 38.0 (t, CH2) ppm.
HR-MS (ESI+) m/z calculated for [C18H19O3]+=[M+H]+: 283.1334; found:
283.1334.
3-(4-Bromophenyl)-5,6-dimethoxy-1H-indene (4gk): GP-1 was carried
out with alcohol 2k (106.5 mg, 0.5` mmol), iodoarene 1g (158.4 mg, 0.5
mmol), Pd(OAc)2 (3.4 mg, 3 mol%), triethylamine (0.2 mL, 1.5 mmol), and
DCE (1.0 mL) for ketone 3gk at 80 C for 24 h, and then with TfOH (0.44
mL, 5 mmol) for indene at rt for 6 h. Purification of the crude material by
silica gel column chromatography (petroleum ether/ethyl acetate 100:0 to
95:5) furnished the indene 4gk (120.8 mg, 73%) as colour less semisolid.
[TLC control (petroleum ether/ethyl acetate 95:5), Rf(2k)=0.45,
Rf(4gk)=0.80, UV detection]. IR (MIR-ATR, 4000–600 cm-1): max=3034,
2912, 1639, 1577, 1475, 1264, 845, 786 cm-1. 1H NMR (CDCl3, 400 MHz):
δ=7.57 (d, 2H, J=8.3 Hz, ArH), 7.44 (d, 2H, J=8.3 Hz, ArH), 7.12 (s, 1H,
ArH), 7.03 (s, 1H, ArH), 6.45 (t, 1H, J=2.0 Hz, C=CH), 3.92 (s, 3H, ArOCH3),
3.88 (s, 3H, ArOCH3), 3.42 (d, 2H, J=2.0 Hz, CH2) ppm. 13C NMR (CDCl3,
3-(4-Isopropylphenyl)-5,6-dimethoxy-1H-indene (4gg): GP-1 was
carried out with alcohol 2g (88 mg, 0.5 mmol), iodoarene 1g (158.4 mg,
0.5 mmol), Pd(OAc)2 (3.4 mg, 3 mol%), triethylamine (0.2 mL, 1.5 mmol),
and DCE (1.0 mL) for ketone 3gg at 80 C for 24 h, and then with TfOH
(0.44 mL, 5 mmol) for indene at rt for 6 h. Purification of the crude material
by silica gel column chromatography (petroleum ether/ethyl acetate 100:0
to 95:5) furnished the indene 4gg (111.8 mg, 76%) as colour less viscous
7
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