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DOI: 10.1055/s-0030-1260955
Synthesis of 1,2-Diarylnaphthalenes by Chemoselective Suzuki-Miyaura Reactions of 2-Bromo-1-(trifluoromethanesulfonyloxy)naphthalene
Publikationsverlauf
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
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References and Notes
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.
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.
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.
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.