B. Schilling, D. E. Kaufmann
FULL PAPER
, 48%), m.p. 201Ϫ202°C. Ϫ IR (KBr, cmϪ1): ν˜ ϭ 3028 (w, ArH), were allowed to react for 24 h. The crude product was purified
1590 (w), 1504 (w), 1393 (m), 1016 (w), 798 (s), 790 (s), 777 (s). Ϫ by flash column chromatography (hexane and hexane/ethyl acetate,
1H NMR (400 MHz, CDCl3): δ ϭ 7.48Ϫ7.61 (m, 8 H, arom. CH), 20:1). The by-product 17 (10 mg, 12%) and the main product 18a
7.64Ϫ7.65 (m, 4 H, arom. CH), 7.91 (d, J ϭ 8.0 Hz, 2 H, arom. (41 mg, 32%) were isolated as white solids.
CH), 7.95 (d, J ϭ 8.4 Hz, 2 H, arom. CH), 8.09 (d, J ϭ 8.4 Hz, 2
2-[4-(1,1Ј-Biphenyl)]-1,1Ј-binaphthyl (17): M.p. 210°C. Ϫ IR
H, arom. CH). Ϫ 13C NMR (50 MHz, CDCl3): δ ϭ 125.44, 125.82,
(KBr, cmϪ1): ν˜ ϭ 3042 and 3027 (w, ArH), 1619 (w), 1596 (w),
126.07, 126.10, 127.05, 127.73 and 128.33 (arom. CH, 14 C), 129.96
1502 (w), 1486 (m), 1365 (w), 819 (s), 802 (m), 783 (m), 766 (s),
(arom. CH, 4 C), 131.63, 133.86, 139.66 and 139.95 (arom. quat.
752 (m), 730 (m). Ϫ 1H NMR (400 MHz, CDCl3): δ ϭ 7.14 (d,
C, 8 C). Ϫ MS (70 eV, EI); m/z (%): 331 (26, Mϩ ϩ 1), 330 (100,
J ϭ 8.4 Hz, 2 H, arom. CH), 7.22Ϫ7.30 (m, 7 H, arom. CH),
Mϩ), 329 (17), 313 (10), 203 (11), 202 (25), 178 (6), 165 (10), 163
7.31Ϫ7.37 (m, 2 H, arom. CH), 7.38Ϫ7.43 (m, 3 H, arom. CH),
(17), 151 (6), 128 (12), 127 (6). Ϫ C26H18 (330.4): calcd. C 94.51,
7.44Ϫ7.49 (m, 3 H, arom. CH), 7.71 (d, J ϭ 8.4 Hz, 1 H, arom.
H 5.49; found C 94.27 H 5.31.
CH), 7.81 (d, J ϭ 8.4 Hz, 1 H, arom. CH), 7.87 (d, J ϭ 8.4 Hz, 1
Coupling of 1-Naphthylboronic Acid (6e) with 4,4Ј-Dibromo-1,1Ј-
biphenyl (15a): Compound 6e (150 mg, 0.872 mmol, 2 equiv.) in 20
ml of ethanol, 15a (136 mg, 0.436 mmol) in 40 ml of toluene and
Pd(PPh3)4 (50 mg, 0.044 mmol, 5 mol%) were allowed to react for
24 h. The crude product was purified by flash column chromatog-
raphy (hexane). The by-product 1,1Ј-binaphthyl (8e) was obtained
as a white solid (21 mg, 9%). The products 16c (32 mg, 20%) and
16d (53 mg, 30%) were isolated as white solids.
H, arom. CH), 7.96 (d, J ϭ 8.4 Hz, 1 H, arom. CH), 8.01 (d, J ϭ
8.4 Hz, 1 H, arom. CH). Ϫ 13C NMR (50 MHz, CDCl3): δ ϭ
125.36, 125.59, 125.73 and 126.06 (arom. CH, 4 C), 126.12 (arom.
CH, 2 C), 126.30 and 126.57 (arom. CH, 2 C), 126.84 (arom. CH,
2 C), 127.09, 127.16, 127.57, 127.84, 128.04, 128.24 and 128.33
(arom. CH, 7 C), 128.61 (arom. CH, 2 C), 129.16 (arom. CH, 1
C), 129.60 (arom. CH, 2 C), 132.61, 133.23, 133.32, 133.59, 135.72,
136.91, 138.80, 138.96, 140.55 and 140.93 (arom. quat. C, 10 C).
Ϫ MS (70 eV, EI); m/z (%): 407 (34, Mϩ ϩ 1), 406 (100, Mϩ), 405
(15), 389 (7), 326 (8), 313 (8), 276 (4), 253 (8), 252 (12), 239 (2),
203 (5), 129 (3), 77 (6). Ϫ C32H22 (406.5): HR MS: calcd. 406.1722;
found 406.1721.
1-[4-(4Ј-Bromo-1,1Ј-biphenyl)]naphthalene (16c): M.p. 165°C. Ϫ
IR (KBr, cmϪ1): ν ϭ 3026 (w, ArH), 1504 (w), 1483 (m), 1394 (m),
˜
1070 (m), 1001 (m), 803 (m), 783 (s), 739 (s). Ϫ 1H NMR (400
MHz, CDCl3): δ ϭ 7.42Ϫ7.63 (m, 10 H, arom. CH), 7.68 (d, J ϭ
8.4 Hz, 2 H, arom. CH), 7.88 (d, J ϭ 8.4 Hz, 1 H, arom. CH), 7.92
(d, J ϭ 8.4 Hz, 1 H, arom. CH), 7.95 (d, J ϭ 8.4 Hz, 1 H, arom.
CH). Ϫ 13C NMR (50 MHz, CDCl3): δ ϭ 121.63 (arom. quat.
CϪBr, 1 C), 125.40, 125.84, 125.90 and 126.12 (arom. CH, 4 C),
126.78 (arom. CH, 2 C), 126.92, 127.81 and 128.33 (arom. CH, 3
C), 128.69 and 130.62 (arom. CH, 4 C), 131.52 (arom. quat. C, 1
C), 131.96 (arom. CH, 2 C), 133.82, 138.85, 139.62, 139.73 and
140.18 (arom. quat. C, 5 C). Ϫ MS (70 eV, EI); m/z (%): 361 (20)
and 359 (30, Mϩ ϩ 1), 360 (100) and 358 (91, Mϩ), 278 (54), 276
(42), 203 (21), 202 (24), 126 (16), 77 (8), 51 (8). Ϫ C22H15Br (359.3):
calcd. C 73.55, H 4.21, Br 22.24; found C 73.56, H 4.19, Br 21.18.
4,4Ј-Bis[2-(1,1Ј-binaphthyl)]-1,1Ј-biphenyl (18a): M.p. 181°C. Ϫ
IR (KBr, cmϪ1): ν˜ ϭ 3050 (m, ArH), 1619 (w), 1592 (w), 1496 (m),
1
1366 (w), 813 (s), 802 (s), 781 (s), 750 (m). Ϫ H NMR (400 MHz,
CDCl3): δ ϭ 7.00Ϫ7.04 (m, 8 H, arom. CH), 7.17Ϫ7.26 (m, 8 H,
arom. CH), 7.31Ϫ7.46 (m, 8 H, arom. CH), 7.63 (d, J ϭ 8.4 Hz, 2
H, arom. CH), 7.76 (d, J ϭ 8.4 Hz, 2 H, arom. CH), 7.82 (d, J ϭ
8.4 Hz, 2 H, arom. CH), 7.93 (d, J ϭ 8.4 Hz, 2 H, arom. CH), 7.99
(d, J ϭ 8.4 Hz, 2 H, arom. CH). Ϫ 13C NMR (50 MHz, CDCl3):
δ ϭ 125.34, 125.58 and 125.69 (arom. CH, 6 C), 125.81 (arom. CH,
4 C), 126.03, 126.27, 126.52, 127.12, 127.54, 127.81, 127.98, 128.23,
128.31 and 129.07 (arom. CH, 20 C), 129.43 (arom. CH, 4 C),
132.56, 133.18, 133.29, 133.54, 135.63, 136.88, 138.11, 138.94 and
140.72 (arom. quat. C, 18 C). Ϫ MS (70 eV, EI); m/z (%): 658 [Mϩ],
644 (2), 574 (1), 513 (1), 458 (1), 402 (1), 329 (9, Mϩ/2), 328 (6),
313 (2), 253 (4), 252 (3), 239 (1). Ϫ C52H34 (658.8): HR MS: calcd.
658.2661; found 658.2661.
4,4Ј-Bis(1-naphthyl)-1,1Ј-biphenyl (16d): M.p. 170°C. Ϫ IR
(KBr, cmϪ1): ν˜ ϭ 3043 and 3026 (w, ArH), 1591 (w), 1494 (w),
1
1394 (m), 1003 (w), 823 (m), 800 (s), 774 (s), 569 (m). Ϫ H NMR
(400 MHz, CDCl3): δ ϭ 7.45Ϫ7.58 (m, 8 H, arom. CH), 7.63 (d,
J ϭ 8.4 Hz, 4 H, arom. CH), 7.82 (d, J ϭ 8.4 Hz, 4 H, arom. CH),
7.89 (d, J ϭ 8.4 Hz, 2 H, arom. CH), 7.93 (d, J ϭ 8.4 Hz, 2 H,
arom. CH), 8.02 (d, J ϭ 8.4 Hz, 2 H, arom. CH). Ϫ 13C NMR (50
MHz, CDCl3): δ ϭ 125.43, 125.82, 126.02 and 126.10 (arom. CH,
8 C), 126.97 (arom. CH, 6 C), 127.74 and 128.33 (arom. CH, 4 C),
130.59 (arom. CH, 4 C), 131.61, 133.86, 139.71, 139.84 and 139.86
Coupling of 2,2Ј-Dibromo-1,1Ј-binaphthyl (3) with 1,1Ј-Biphenyl-
4,4Ј-diboronic Acid Bispinacol Ester (15b): Compound 3 (412 mg,
1.000 mmol, 2 equiv.) in 20 ml of toluene, 15b (203 mg, 0.500
mmol) in 10 ml of ethanol and Pd(PPh3)4 (116 mg, 0.100 mmol,
10 mol%) were allowed to react for 24 h. The crude product was
purified by flash column chromatography (hexane and hexane/ethyl
acetate, 20:1). The by-product 1,1Ј-binaphthyl (8e) was obtained
as a white solid (24 mg, 9%). The main product 4,4Ј-bis[2-(1,1Ј-
binaphtyl)]-1,1Ј-biphenyl (18a, 134 mg, 41%) was isolated as a
white solid, spectroscopic data for 18a see above.
(arom. quat. C, 10 C). Ϫ MS (70 eV, EI); m/z (%): 407 (37, Mϩ
ϩ
1), 406 (100, Mϩ), 405 (6), 389 (6), 276 (4), 263 (1), 252 (1), 203
(19), 202 (21), 201 (8), 200 (8), 165 (2), 126 (1), 77 (1), 63 (1). Ϫ
C32H22 (406.5): calcd. C 94.55, H 5.45; found C 93.49, H 5.40: HR
MS: calcd: 406.1722; found 406.1721.
Coupling of 1-[4-(4Ј-Bromo-1,1Ј-biphenyl)]naphthalene (16c)
with 1-Naphthylboronic Acid Pinacol Ester (6f): Compound 16c (10
mg, 0.028 mmol) in 4 ml of toluene, 1 equiv. of 6f (7 mg, 0.028
mmol) in 4 ml of ethanol and Pd(PPh3)4 (3 mg, 0.0028 mmol, 10
mol%) were allowed to react for 24 h. The reaction was monitored
by gas chromatography. The starting material was quantitatively
transformed into the product 4,4Ј-bis(1-naphthyl)-1,1Ј-biphenyl
(16d), spectroscopic data for 16d see above.
1,1Ј-Biphenyl-4,4Ј-diboronic Acid Bispinacol Ester (15b): To a
solution of 4,4Ј-dibromo-1,1Ј-biphenyl (15a, 3.000 g, 9.62 mmol)
in 30 ml THF, was added a 1.6 solution of n-butyllithium (13.22
ml, 21.15 mmol) at Ϫ40°C. After stirring for 1 h, the mixture was
cooled to Ϫ78°C and added to a solution of 5 equiv. of trimethyl
borate (5.36 ml, 48.07 mmol) in 80 ml of THF. The reaction mix-
ture was allowed to warm to room temperature overnight. The sol-
vents were evaporated under reduced pressure. The solid residue
Coupling of 1,1Ј-Binaphthyl-2-boronic Acid Pinacol Ester (2) with was dissolved in 50 ml of diethyl ether and was then hydrolyzed
4,4Ј-Dibromo-1,1Ј-biphenyl (15a): Compound 2 (148 mg, 0.388
mmol, 2 equiv) in 20 ml of ethanol, 15a (61 mg, 0.194 mmol) in
20 ml of toluene and Pd(PPh3)4 (45 mg, 0.049 mmol, 10 mol%)
with 1 hydrochloric acid. The product was extracted with 250 ml
of diethyl ether, which was washed with a saturated aqueous so-
dium hydrogen carbonate solution and water. The crude product
708
Eur. J. Org. Chem. 1998, 701Ϫ709