Month 2013
Suzuki–Miyaura Cross‐Coupling Reaction of Naphthyl Triflate with Indole Boronic Acids
3‐{7‐[5‐(4‐Methoxyphenyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐
6‐fluoro‐1H‐indole (13d). oil; IR (KBr, cm−1): v = 3297.4,
3059.9, 2916.3, 2851.0, 2229.8, 1678.9, 1664.1, 1619.5,
1593.2, 1563.7, 1534.9, 1481.4, 1444.9, 1316.1, 1286.9,
1190.1, 1014.3, 830.9, 743.1, 702.0, 672.1, 623.5; 1H‐NMR
(CDCl3): δ = 3.83 (3H, s), 6.99 (1H, s), 7.08–7.86 (14H, m),
10.36 (1H, brs); 13C‐NMR (DMSO‐d6): δ = 56.2, 108.1, 114.2,
118.2, 126.1, 126.4, 126.7, 127.9, 128.0, 129.0, 129.1, 132.3,
137.6, 144.0, 146.1, 146.5, 150.8, 163.7; MS (EI) m/z: (M++1)
439.62; Anal. Calcd. for C28H19FN2O2: C, 77.43; H, 4.40; N,
6.48; found: C, 77.39; H, 4.37; N, 6.52.
3‐{7‐[5‐(4‐Chlorophenyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐
6‐chloro‐1H‐indole (13j). Yield: 79%; m.p.: 236–237°C; IR
(KBr, cm−1): v = 3248.0, 3027.9, 2931.0, 1729.1, 1625.7,
1529.3, 1494.8, 1444.4, 1225.9, 1213.4, 1182.6, 745.9, 709.4;
1H‐NMR (CDCl3): δ = 7.02 (1H, s), 7.11–7.88 (14H, m),
10.41 (1H, brs); 13C‐NMR (CDCl3): δ = 100.2, 108.0, 1112.8,
120.6, 121.8, 122.9, 124.9, 125.8, 128.9, 129.2, 130.6, 132.6,
133.9, 134.2, 138.7, 139.4, 141.5, 145.5, 148.9, 150.1, 153.6;
MS (EI) m/z: (M++2) 457.52; Anal. Calcd. for C27H16Cl2N2O:
C, 71.22; H, 3.55; Cl, 15.57; N, 6.15; found: C, 71.21; H,
3.50; Cl, 15.59; N, 6.21.
3‐{7‐[5‐(3‐Methoxyphenyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐
6‐fluoro‐1H‐indole (13e). oil; IR (KBr, cm−1): v = 3286.2,
3063.9, 2916.3, 2853.0, 2223.8, 1679.9, 1611.5, 1594.2,
1562.7, 1532.9, 1487.4, 1445.9, 1313.1, 1286.7, 1192.1,
3‐{7‐[5‐(4‐Methoxyphenyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐
6‐chloro‐1H‐indole (13k). Semi solid; IR (KBr, cm−1): v =
3265.2, 3062.9, 2920.3, 2854.3, 2232.4, 1675.5, 1658.3,
1614.5, 1598.2, 1563.7, 1531.9, 1486.4, 14454.9, 1317.1,
1282.4, 1191.3, 1018.2, 831.0, 745.1, 712.0, 623.5; 1H‐NMR
(CDCl3): δ = 3.92 (3H, s), 6.97 (1H, s), 7.08–7.86 (14H, m),
10.39 (1H, brs); 13C‐NMR (DMSO‐d6): δ = 56.3, 108.0,
114.5, 118.4, 126.6, 126.8, 126.2, 127.4, 128.6, 129.8, 129.1,
132.7, 137.5, 144.2, 146.3, 146.0, 150.7, 163.4; MS (EI) m/z:
(M++2) 452.26; Anal. Calcd. for C28H19ClN2O2: C, 74.58; H,
4.26; Cl, 7.86; N, 6.21; found: C, 74.45; H, 4.30; Cl, 7.86;
N, 6.25.
3‐{7‐[5‐(p‐Tolyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐6‐chloro‐1H‐
indole (13l). Yield: 85%; m.p.: 125–127°C; IR (KBr, cm−1): v =
3245.2, 3084.8, 3048.9, 2962.8, 2927.1, 2223.1, 1645.4, 1623.3,
1594.1, 1567.6, 1485.3, 1445.7, 1306.8, 1271.2, 1187.0, 1063.2,
1018.2, 814.2, 743.0, 700.6; 1H‐NMR (CDCl3): δ = 2.43
(3H, s), 7.08 (1H, s), 7.11–7.97 (14H, m), 10.38 (1H, brs);
13C‐NMR (DMSO‐d6): δ = 20.8, 101.6, 108.7, 111.4, 114.6,
118.8, 126.5, 127.7, 128.5, 129.3, 132.6, 144.5, 146.4, 146.8,
152.7; MS (EI) m/z: (M++2) 436.34; Anal. Calcd. for
C28H19ClN2O: C, 77.35; H, 4.45; Cl, 8.15; N, 6.44; found: C,
77.41; H, 4.41; Cl, 8.12; N, 6.49.
3‐{7‐[5‐(4‐Nitrophenyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐6‐fluoro‐
1H‐indole (13m). Yield: 85%; m.p.: 163–165°C; IR (KBr, cm−1):
v = 3236.0, 2925.2, 2238.1, 1624.1, 1598.5, 1566.1, 1534.2,
1481.3, 1284.3, 1194.6, 1076.1, 1018.7, 712.4, 684; 1H‐NMR
(DMSO‐d6): δ = 7.01 (1H, s), 7.08–7.79 (14H, m), 10.41 (1H,
brs); 13C‐NMR (DMSO‐d6): δ = 99.8, 108.6, 114.4, 115.9, 119.7,
121.3, 124.8, 126.2, 132.2, 142.6, 145.6, 148.1, 152.9, 153.4; MS
(EI) m/z: (M++2) 467.25; Anal. Calcd. for C27H16ClN3O3: C,
69.62; H, 3.42; Cl, 7.62; N, 9.02; found: C, 69.62; H, 3.31; Cl,
7.62; N, 9.08.
1
1013.3, 834.9, 745.1, 702.0, 675.1, 629.5; H‐NMR (CDCl3): δ
= 3.89 (3H, s), 6.92 (1H, s), 7.08–7.86 (14H, m), 10.39 (1H,
brs); 13C‐NMR (DMSO‐d6): δ = 56.8, 109.0, 114.6, 118.3,
125.8, 126.4, 126.7, 127.9, 128.2, 128.9, 129.6, 133.0, 137.5,
144.6, 146.3, 145.5, 150.7, 163.9; MS (EI) m/z: (M++1) 439.34;
Anal. Calcd. for C28H19FN2O2: C, 77.43; H, 4.40; N, 6.48;
found: C, 77.43; H, 4.39; N, 6.50.
3‐{7‐[5‐(p‐Tolyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐6‐fluoro‐
1H‐indole (13f). Yield: 89%; m.p.: 165–167°C; IR (KBr,
cm−1): v = 3246.2, 3083.8, 3047.9, 2960.8, 2926.1, 2226.1,
1647.4, 1622.3, 1593.1, 1563.6, 1484.3, 1444.7, 1308.8,
1274.2, 1188.0, 1065.2, 1008.2, 802.2, 743.0, 700.6, 621.9;
1H‐NMR (CDCl3): δ = 2.56 (3H, s), 7.10 (1H, s), 7.15–7.96
(14H, m), 10.42 (1H, brs); 13C‐NMR (DMSO‐d6): δ = 19.8,
101.3, 108.6, 110.5, 114.2, 118.3, 126.4, 126.7, 128.0, 129.1,
132.4, 144.1, 146.0, 146.6, 152.7; MS (EI) m/z: (M++1)
419.34; Anal. Calcd. for C28H19FN2O: C, 80.38; H, 4.59; N,
6.69; found: C, 80.41; H, 4.61; N, 6.53.
3‐{7‐[5‐(o‐Tolyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐6‐fluoro‐1H‐
indole (13g). Yield: 84%; m.p.: 189–191°C; IR (KBr, cm−1): v =
3245.2, 3084.8, 3046.4, 2961.7, 2923.3, 2226.51, 1647.4, 1622.3,
1594.1, 1567.6, 1489.3, 1442.7, 1304.8, 1277.2, 1189.0, 1063.2,
1
1021.2, 802.2, 745.0, 704.6, 622.9; H‐NMR (CDCl3): δ = 2.62
(3H, s), 7.09 (1H, s), 7.08–7.82 (14H, m), 10.39 (1H, brs); 13C‐
NMR (DMSO‐d6): δ = 19.9, 100.3, 101.6, 108.3, 110.7, 114.9,
118.1, 126.3, 126.7, 128.7, 129.0, 132.4, 144.3, 146.6, 146.7,
152.7; MS (EI) m/z: (M++1) 419.26; Anal. Calcd. for C28H19FN2O:
C, 80.38; H, 4.59; N, 6.69; found: C, 80.43; H, 4.62; N, 6.58.
3‐{7‐[5‐(4‐Nitrophenyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐
6‐fluoro‐1H‐indole (13h). Brown oil, IR (KBr, cm−1): v = 3247.0,
2922.2, 2221.1, 1621.1, 1595.5, 1565.1, 1536.8, 1479.7, 1288.4,
1
1192.1, 1071.1, 1009.7; H‐NMR (DMSO‐d6): δ = 6.94 (1H, s),
Acknowledgment. The authors are thankful to the University Grants
Commission, New Delhi, for financial help.
7.01–7.85 (14H, m), 10.36 (1H, brs); 13C‐NMR (DMSO‐d6): δ =
98.0, 115.1, 115.6, 118.7, 120.4, 123.5, 125.7, 132.0, 142.4, 145.3,
147.1, 151.9, 153.3; MS (EI) m/z: (M++1) 450.86; Anal. Calcd. for
C27H16FN3O3: C, 72.18; H, 3.64; N, 9.36; found: C, 72.13; H,
3.62; N, 9.38.
REFERENCES AND NOTES
3‐{7‐[5‐(4‐Fluorophenyl)‐oxazole‐2‐yl]‐naphthalene‐2‐yl}‐
6‐fluoro‐1H‐indole (13i). Yield 92%; m.p.: 210–212°C, IR
(KBr, cm−1): v = 3248.0, 2954.2, 2232.1, 1624.1, 1674.2,
1585.5, 1572.1, 1538.8, 1454.7, 1265.4, 1192.1, 1071.1,
1009.7; 1H‐NMR (DMSO‐d6): δ = 6.94 (1H, s), 7.01–7.85
(14H, m), 10.36 (1H, brs); 13C‐NMR (DMSO‐d6): δ = 98.2,
115.4, 115.8, 118.1, 120.7, 123.3, 124.7, 133.0, 142.2, 143.5,
145.1, 150.9, 153.3, 162.4; MS (EI) m/z: (M++1) 423.79; Anal.
Calcd. for C27H16F2N2O: C, 76.77; H, 3.86; N, 6.65; found: C,
77.83; H, 3.92; N, 6.72.
[1] Sing, H.; Yadav, L. D.; Bhattacharya, B. K. J Indian Chem Soc
1979, 56, 1013; (b) Desai, N. Indian J Chem B 1993, 32, 343; (c)
Upadhyay, D. S.; Vansdadia, R. N.; Baxi, A. J. Indian J Chem 1990,
29, 793; (d) Feng, X. M.; Liu, X. C.; Zhang, Z. Y. Chin J Appl Chem
1991, 8, 28; (e) Rao, K. V.; Biemann, K.; Woodword, R. B. J Am Chem
Soc 1963, 85, 2532.
[2] Kambara, T.; Koshida, T.; Saito, N.; Kuwajima, I.; Kubata, K.;
Yamamoto, T. Chem Lett 1992,583.
[3] Meyer, T. Acc Chem Res 1989, 22, 165.
[4] Zhang, Z. Y.; Chen, X.; Wei, L. L.; Ma, Z. L. Chem Res Chin
Univ 1991, 7, 129.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet