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Synlett 2011(13): 1827-1830  
DOI: 10.1055/s-0030-1260955
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of 1,2-Diarylnaphthalenes by Chemoselective Suzuki-Miyaura Reactions of 2-Bromo-1-(trifluoromethanesulfonyloxy)naphthalene

Zahid Hassana, Munawar Hussaina, Peter Langer*a,b
a Institut für Chemie, Universität Rostock, Albert Einstein Str. 3a, 18059 Rostock, Germany
b Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert Einstein Str. 29a, 18059 Rostock, Germany
Fax: +49(381)4986412; e-Mail: peter.langer@uni-rostock.de;
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Received 14 March 2011
Publikationsdatum:
14. Juli 2011 (online)

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Abstract

Suzuki-Miyaura reactions of 2-bromo-1-(trifluoromethanesulfonyloxy)naphthalene, readily available from 1-tetralone in two steps, afforded a variety of 1,2-diarylnaphthalenes. The reactions proceed with excellent chemoselectivity in favor of the bromide position, while the triflate remained unattacked.

Key words

catalysis - palladium - Suzuki-Miyaura reaction - naphthalene - chemoselectivity

    References and Notes

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14

Synthesis of 2-Bromonaphth-1-ol (5)
A benzene suspension (30 mL) of 1-tetralone (4, 1.8 mL, 13.7 mmol), NBS (5.4 g, 30.2 mmol), and (PhCOO)2 (0.17 g, 5mol%) was refluxed under Argon atmosphere for 4 h and then cooled to 20 ˚C. To the reaction mixture was added Et3N (1 mL), and the solvent was removed in vacuo. The reaction mixture was diluted with H2O and extracted with CH2Cl2 (3 × 25 mL). The combined organic layers were dried (Na2SO4), filtered, and the filtrate was concentrated in vacuo. The residue was purified by flash chromatography (silica gel, heptane-EtOAc) to give 5 as a colorless solid (2.57 g, 84%). R f  = 0.54 (heptane-EtOAC = 4:1). ¹H NMR (250 MHz, CDCl3): δ = 5.89 (s, 1 H, OH), 7.24 (d, 1 H, J = 8.8 Hz), 7.38-7.41 (d, 1 H, J = 8.8 Hz), 7.43-7.46 (m, 2 H), 7.66-7.75 (m, 1 H), 8.12-8.19 (m, 1 H). ¹³C NMR (75.5 MHz, CDCl3): δ = 104.0 (C), 121.3, 122.2, 124.1 (CH), 124.4 (C), 124.8, 127.5, 128.3 (CH), 133.7, 148.1 (C). IR (KBr): ν = 3400 (s), 3051, 1958, 1931, 1883, 1877, 1624 (w), 1586, 1574 (m), 1504 (w), 1453, 1396, 1384, 1347, 1240, 1212, 1202, 1140, 1126, 1054, 1021, 876, 856 (m), 829, 792, 768, 736 (s), 716, 641, 600, 561 (m) cm-¹. GC-MS (EI, 70 eV): m/z (%) = 222 (98) [M]+, 115 (92). HRMS (EI, 70 eV): m/z calcd for C10H7BrO [M]+: 221.96803; found: 221.96799.

15

Synthesis of 2-Bromonaphth-1-yl Trifluoromethanesulfonate (6) To a solution of 5 (2.4 g, 10.8 mmol) in CH2Cl2 (25 mL) was added pyridine (1.8 mL, 21.6 mmol) at 20 ˚C under an argon atmosphere. After stirring for 10 min at 0 ˚C, Tf2O (2.7 mL, 16.4 mmol) was added. The mixture was allowed to warm to 20 ˚C and stirred for further 6 h. The reaction mixture was filtered, and the filtrate was concentrated in vacuo. The residue was directly purified by chromatography without aqueous workup (flash silica gel, heptane-EtOAc) to give 6 as a light yellow oil (3.53 g, 92%). R f  = 0.71 (heptane-EtOAc, 4:1). ¹H NMR (300 MHz, CDCl3): δ = 7.56-7.69 (m, 4 H), 7.83 (d, 1 H, J = 7.8 Hz), 8.13 (d, 1 H, J = 8.1 Hz). ¹9F NMR (282.4 MHz, CDCl3): δ = -73.0. ¹³C NMR (75.5 MHz, CDCl3): δ = 114.1 (C), 118.5 (q, J F,C = 321.0 Hz, CF3), 121.2, 127.5 (CH), 127.9 (C), 128.1, 128.5, 129.4, 129.9 (CH), 133.7, 142.6 (C). IR (KBr): ν = 1589, 1501, 1457 (m), 1408 (s), 1370, 1365 (m), 1203, 1181 (s), 1124 (s), 1032, (m)1018, 890, 801, 761 (s), 743, 703, 665, 616, 587, (m) cm-¹. GC-MS (EI, 70 eV): m/z (%) = 354 (100) [M]+, 223 (52). HRMS (EI, 70 eV): m/z calcd for C11H6BrF3O3S: 353.91731 [M]+; found: 353.91711.

16

General Procedure for Suzuki-Miyaura Reactions
A 1,4-dioxane (5 mL per 1 mmol) solution of 6 or 9a-e (1.0 equiv), K3PO4 (1.5 equiv per cross-coupling step), Pd(PPh3)4 (5 mol%), and arylboronic acid 3 (1.0-1.1 equiv per cross-coupling step) was stirred at 90-110 ˚C for 4 h. After cooling to 20 ˚C, H2O was added. The organic and the aqueous layers were separated, and the latter was extracted with CH2Cl2 (15 × 3 mL). The combined organic layer was dried (Na2SO4), filtered, and the filtrate was concentrated in vacuo. The residue was purified by column chromatography.

17

Synthesis of 2-(4-Fluorophenyl)naphth-1-yl Trifluoromethanesulfonate (9e)
Starting with 6 (200 mg, 0.73 mmol), 4-fluorophenylboronic acid 7e (102 mg, 0.73 mmol), Pd(PPh3)4 (42 mg, 5 mol%), K3PO4 (232 mg, 1.5 mmol), and 1,4-dioxane (5 mL), 9e was isolated as a highly viscous oil (229 mg, 85%). R f  = 0.51 (heptane-EtOAc, 4:1). ¹H NMR (300 MHz, CDCl3): δ = 7.05-7.15 (m, 2 H), 7.38-7.45 (m, 3 H), 7.49-7.62 (m, 2 H), 7.80-7.59 (m, 2 H), 8.09 (d, 1 H, J = 8.4 Hz, ArH). ¹9F NMR (282.4 MHz, CDCl3): δ = -113.2, -74.0. ¹³C NMR (62.9 MHz, CDCl3): δ = 115.6 (d, J F,C = 21.4 Hz, 2 CH), 117.1 (q, J F,C = 316.2 Hz, CF3), 119.7 (C), 121.7, 127.3, 128.0 (CH), 128.2 (d, J F,C = 2.6 Hz, 2 CH), 128.6, 131.4, 131.6 (CH), 132.3, 132.4, 134.1, 141.9 (C), 161.9 (d, J F,C = 248.5 Hz, CF). IR (KBr): ν = 2961, 1606 (w), 1513, 1498 (m), 1405 (s), 1341 (w), 1201 (s), 1159 (m), 1132 (s), 1088, 1018, 1007 (m), 894 (s), 867 (m), 816, 804 (s), 764 (m), 749 (s), 703, 683, 622, 598, 556, (m) cm-¹. GC-MS (EI, 70 eV): m/z (%) = 370 (19) [M+], 237 (100), 209 (51), 183 (12). HRMS (EI, 70 eV): m/z calcd for C17H10F4O3S [M]+: 370.02813; found: 370.02763.

18

Synthesis of 2-(4-Fluorophenyl)-1-( m -tolyl)naphthalene (10e)
Starting with 9e (100 mg, 0.27 mmol), 3-tolylboronic acid (40 mg, 0.29 mmol), Pd(PPh3)4 (16 mg, 5 mol%), K3PO4 (86 mg, 0.41 mmol), and 1,4-dioxane (5 mL), 10e was isolated as a highly viscous oil (65 mg, 77%). R f  = 0.44 (heptane-EtOAc, 4:1). ¹H NMR (300 MHz, CDCl3): δ = 2.2 (s, 3 H, CH3), 6.75-6.91 (m, 4 H), 7.00-7.05 (m, 3 H), 7.10 (t, 1 H, J = 7.4 Hz), 7.28-7.40 (m, 2 H), 7.43 (d, 1 H, J = 8.6 Hz), 7.58 (br d, 1 H, J = 8.5 Hz), 7.81 (d, 2 H, J = 8.2 Hz). ¹9F NMR (282.4 MHz, CDCl3): δ = -116.6. ¹³C NMR (75.5 MHz, CDCl3): δ = 114.5 (d, J F,C = 21.3 Hz, 2 CH), 125.8, 126.3, 126.9, 127.6, 127.8, 127.9, 128.1, 128.5, 131.5, 131.6, 132.1 (CH), 132.7, 132.8, 137.2, 137.4, 137.9, 138.1 (d, J F,C = 3.3 Hz, C), 138.7 (C), 161.5 (d, J F,C = 245.6 Hz, CF). IR (KBr): ν = 3050, 2920 (m), 2852 (w), 1601 (m), 1499 (s), 1457 (m), 1234 (w), 1218 (s), 1155, 1092, 1023 (m), 962 (w), 863, 841 (m), 817, 803, 778, 743, 713, 693 (s), 653, 544 (m) cm-¹. GC-MS (EI, 70 eV): m/z (%) = 312 (100) [M+], 222 (55), 204 (7). HRMS (EI, 70 eV): m/z calcd for C23H17F [M]+: 312.13143; found: 312.13133.