C. I. Schilling, O. Plietzsch, M. Nieger, T. Muller, S. Bräse
FULL PAPER
2
1096 (w), 1018 (vw), 1005 (vw), 918 (vw), 853 (vw), 825 (w), 774
(w), 753 (vw), 704 (vw), 657 (vw), 564 (vw), 515 (vw), 476 (vw),
417 (vw) cm–1. MS (FAB, 3-NBA): m/z (%) = 968 (25) [M+], 909
(+, d, JC,F = 21.5 Hz, Ar-C-3Ј), 125.6 (+, Ar-C-2), 127.0 (+, Ar-
3
C-3), 128.5 (+, d, JC,F = 8.0 Hz, Ar-C-2Ј), 131.3 (Cq, Ar-C-4),
137.6 (d, 1JC,F = 138 Hz, Cq, Ar-C-4Ј), 148.3 (d, JC,F = 6.0 Hz, Cq,
Ar-C-1Ј), 157.0 (Cq, Ar-C-1) ppm. 19F NMR (376 MHz, CDCl3):
(26) [M+ – C3H7O], 783 (33) [M+ – C7H14O4], 729 (44) [M+
–
C16H15O2], 154 (100). HRMS (C65H60O8): calcd. 968.4288; found
968.4282.
δ = –115.8 (s, Ar-F) ppm. IR (DRIFT): ν = 3432 (br., vw), 3030
˜
(vw), 2927 (vw), 2851 (vw), 1887 (vw), 1602 (vw), 1497 (w), 1356
(vw), 1222 (w), 1158 (vw), 1096 (vw), 1007 (vw), 820 (w), 700 (vw),
577 (vw), 533 (vw) cm–1. MS (FAB, 3-NBA): m/z (%) = 818/817/
1,3,5,7-Tetrakis(4Ј-methoxy-[1,1Ј-biphenyl]-4-yl)adamantane (3b):
The Suzuki coupling was carried out according to the general pro-
816 (34/65/97) [M + H]+, 802 (15) [M+ – CH2], 722 (50) [M+
C6H4F]. HRMS (C58H44F4): calcd. 816.3379; found 816.3382.
–
cedure
A
using (4-methoxyphenyl)boronic acid (148 mg,
1.68 mmol, 8.00 equiv.) in dry toluene/EtOH/H2O (25 mL, 11:2:1).
The product 3b was purified after the reaction by column
chromatography (3ϫ 20 cm, cyclohexane/CH2Cl2, 2:1) and isolated
as a brownish solid (151 mg, 180 μmol, 84%); m.p. 350 °C (dec.).
Rf = 0.26 (cyclohexane/CH2Cl2, 1:2) 1H NMR (400 MHz, CDCl3):
δ = 2.28 (s, 12 H, Ad-CH2), 3.85 (s, 12 H, OCH3), 6.98 (d, J =
8.8 Hz, 8 H, Ar-H-3Ј), 7.56 (d, J = 8.8 Hz, Ar-H-2Ј), 7.57 (s, 16 H,
Ar-H-2/3) ppm. 13C NMR (100 MHz, CDCl3): δ = 39.0 (Cq, Ad-
C), 47.2 (–, Ad-CH2), 55.2 (+, OCH3), 114.0 (+, Ar-C-3Ј), 125.3
(+, Ar-C-2), 126.5 (+, Ar-C-3), 127.9 (+, Ar-C-2Ј), 133.3 (Cq, Ar-
C-1Ј), 138.5 (Cq, Ar-C-4), 147.7 [Cq, Ar(Ad)-C-1], 158.9 [Cq, Ar(-
Tetrakis(4Ј-fluoro-[1,1Ј-biphenyl]-4-yl)methane (5c): The reaction
was carried out following the general procedure B with (4-fluo-
rophenyl)boronic acid (67.9 mg, 0.490 mmol, 8.00 equiv.). After
column chromatography purification (3ϫ 20 cm, cyclohexane/
EtOAc, 10:1), the product 5c was isolated as a white solid (21.0 mg,
30.1 μmol, 50%); m.p. 268 °C (dec.). Rf = 0.39 (cyclohexane/
EtOAc, 25:1). 1H NMR (400 MHz, CDCl3): δ = 7.08–7.15 (m, 8
H, Ar-H-3Ј), 7.39 (d, J = 8.4 Hz, 8 H, Ar-H-2), 7.49 (d, J = 8.4 Hz,
8 H, Ar-H-3), 7.54–7.60 (m, 8 H, Ar-H-2Ј) ppm. 13C NMR
(100 MHz, CDCl3): δ = 64.1 [Cq, C(Ar)4], 115.7 (+, JC,F = 21.4 Hz,
Ar-C-3Ј), 126.1 (+, Ar-C-3) 128.5 (+, JC,F = 8.0 Hz, Ar-C-2Ј), 131.5
(+, Ar-C-2), 136.6 (JC,F = 3.2 Hz, Cq, Ar-C-1Ј), 137.8 (Cq, Ar-C-
4), 145.7 (Cq, Ar-C-1), 162.5 (JC,F = 246.4 Hz, Cq, Ar-C-4Ј) ppm.
OCH )-C-4Ј] ppm. IR (DRIFT): ν = 3029 (m), 2999 (w), 2928 (m),
˜
3
2834 (m), 2538 (w), 2052 (w), 1883 (w), 1608 (m), 1580 (w), 1557
(w), 1522 (m), 1497 (m), 1464 (m), 1441 (m), 1396 (w), 1353 (m),
1287 (m), 1247 (m), 1204 (m), 1178 (m), 1111 (w), 1041 (m), 1014
(m), 1000 (m), 951 (w), 893 (w), 820 (m), 783 (w), 741 (w), 718 (w),
698 (m), 644 (w), 585 (m), 536 (m), 4141 (vw) cm–1. MS (FAB, 3-
NBA): m/z (%) = 866 (35) [M + 2H]+, 865 (74) [M + H]+. HRMS
(C62H56O4): calcd. 864.4178; found 864.4181.
IR (ATR): ν = 2957 (w), 2923 (w), 2853 (w), 1732 (vw), 1598 (w),
˜
1519 (w), 1492 (m), 1377 (w), 1260 (w), 1224 (m), 1199 (w), 1158
(m), 1096 (m), 1006 (m), 850 (w), 806 (m), 743 (w), 713 (w), 703
(m), 583 (vw), 554 (w), 510 (m), 450 (w), 405 (vw) cm–1.
Tetrakis([1,1Ј-biphenyl]-4-yl)adamantane (3d): The reaction was car-
ried out according to the general procedure A using phenylboronic
acid (205 mg, 1.68 mmol, 8.00 equiv.) in dry toluene/EtOH/H2O
(25 mL, 11:2:1). The product 3d was purified after the reaction by
column chromatography (3ϫ 20 cm, cyclohexane/CH2Cl2, 50:1)
and isolated as a grey solid (55.0 mg, 70.0 μmol, 35%); m.p. 287 °C.
Rf = 0.32 (cyclohexane/CH2Cl2, 50:1). 1H NMR (400 MHz,
CDCl3): δ = 2.31 (s, 12 H, Ad-CH2), 7.35 (d, J = 7.4 Hz, 8 H, Ar-
H-2), 7.45 (t, J = 7.6 Hz, 8 H, Ar-H-3), 7.61–7.63 (m, 20 H, Ph-H-
2Ј/3Ј/4Ј) ppm. 13C NMR (100 MHz, CDCl3): δ = 39.2 (Cq, Ad-C),
47.4 (–, Ad-CH2), 125.5 (+, Ar-C-2), 127.1 (+, Ar-C-2Ј), 127.1 (+,
Ar-C-3Ј/4Ј), 128.7 (+, Ar-C-3), 139.1 (Cq, Ar-C-4), 140.8 (Cq, Ar-
Tetrakis(4Ј-methoxy-[1,1Ј-biphenyl]-4-yl)methane (5b): The reaction
was carried out following the general procedure B with (4-meth-
oxyphenyl)boronic acid (99.0 mg, 0.480 mmol, 8.00 equiv.). After
the purification by column chromatography (3ϫ 20 cm, cyclohex-
ane/EtOAc, 4:1), the product 5b was isolated as a brown solid
(36.0 mg, 48.3 μmol, 79%); m.p. 242 °C (dec.). Rf = 0.34 (cyclohex-
1
ane/EtOAc, 3:1). H NMR (400 MHz, CDCl3): δ = 3.85 (s, 12 H,
OCH3), 6.97 (d, J = 8.7 Hz, 8 H, Ar-H-3Ј), 7.37 (d, J = 8.4 Hz, 8
H, Ar-H-2), 7.50 (d, J = 8.4 Hz, 8 H, Ar-H-3), 7.56 (d, J = 8.7 Hz,
8 H, Ar-H-2Ј) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.3 (+,
OCH3), 64.0 [Cq, C(Ar)4], 114.2 (+, Ar-C-3Ј), 125.7 (+, Ar-C-3),
128.0 (+, Ar-C-2), 131.5 (+, Ar-C-2Ј), 133.1 (Cq, Ar-C-1Ј), 138.1
(Cq, Ar-C-4), 145.3 (Cq, Ar-C-1), 159.1 (Cq, Ar-C-4Ј) ppm. IR
C-1Ј), 148.4 (C , Ar-C-1) ppm. IR (DRIFT): ν = 3056 (w), 3025
˜
q
(m), 2925 (m), 2896 (w), 2849 (w), 1486 (m), 842 (m), 763 (m), 696
(m) cm–1. MS (FAB, 3-NBA): m/z (%) = 744 (100) [M+], 668 (26)
[M+ – C6H5], 695 (11) [M+ – C4H2], 745 (71) [M + H]+. HRMS
(C58H48): calcd. 744.3756; found 744.3759.
(ATR): ν = 2921 (w), 2848 (w), 1707 (vw), 1604 (w), 1579 (vw),
˜
1522 (vw), 1490 (w), 1440 (w), 1393 (vw), 1290 (w), 1246 (w), 1208
(w), 1175 (w), 1113 (w), 1067 (w), 1040 (w), 1000 (w), 818 (m), 806
(m), 709 (w), 702 (w), 588 (vw), 557 (vw), 515 (w) cm–1. MS (FAB,
3-NBA): m/z (%) = 744 (6) [M+], 607 (19) [M+ – C8H9O2], 147 (100)
[C10H11O+]. HRMS (C53H44O4): calcd. 744.3240; found 744.3243.
Tetrakis([1,1Ј-biphenyl]-4-yl)methane (5d): The reaction was carried
out following general procedure
B with phenylboronic acid
(58.5 mg, 0.49 mmol, 8.00 equiv.). After purification by column
chromatography (3ϫ 20 cm, cyclohexane/EtOAc, 25:1), the prod-
uct 5d was isolated as a brown solid (23 mg, 0.07 mmol, 61%);
m.p. 221 °C (dec.). Rf = 0.40 (cyclohexane/EtOAc, 25:1). 1H NMR
(400 MHz, CDCl3): δ = 7.34 (t, J = 7.2 Hz, 4 H, Ar-H-4Ј), 7.40–
7.47 (m, 16 H, Ar-H-2/–3), 7.57 (d, J = 8.5 Hz, 8 H, Ar-H-3Ј), 7.64
(d, J = 7.2 Hz, 8 H, Ar-H-2Ј) ppm. 13C NMR (100 MHz, CDCl3):
δ = 64.2 [Cq, C(Ar)4], 126.2 (+, Ar-C-3), 127.0 (+, Ar-C-2Ј), 127.2
(+, Ar-C-4Ј), 128.7 (+, Ar-C-3Ј), 131.5 (+, Ar-C-2), 138.6 (Cq, Ar-
1,3,5,7-Tetrakis(4Ј-fluoro-[1,1Ј-biphenyl]-4-yl)adamantane (3c): The
reaction was carried out against the general procedure A using
1,3,5,7-tetrakis(4-iodophenyl)adamantane (1, 149 mg, 160 μmol,
1.00 equiv.), Pd(PPh3)4 (23.5 mg, 20.0 μmol. 0.130 equiv.), K2CO3
(281 mg, 2.02 mmol, 13.0 equiv.) and (4-fluorophenyl)boronic acid
(175 mg, 1.24 mmol, 8.00 equiv.) in dry toluene/EtOH/H2O
(25 mL, 11:2:1). After 24 h, further (4-fluorophenyl)boronic acid
(44.8 mg, 320 μmol, 2.00 equiv.) was added and refluxed for an ad-
ditional day. The reaction mixture was then purified by column
chromatography (3ϫ 20 cm, cyclohexane/CH2Cl2, 10:1) and the
product 3c was isolated as a white solid (61.8 mg, 80.0 μmol, 49%);
m.p. 350 °C (dec.). Rf = 0.32 (cyclohexane/CH2Cl2, 10:1). 1H NMR
(400 MHz, CDCl3): δ = 2.28 (s, 12 H, Ad-CH2), 7.13 (d, J = 8.7 Hz,
8 H, Ar-H-2Ј), 7.55–7.61 (m, 24 H, Ar-H-2/3/3Ј) ppm. 13C NMR
(100 MHz, CDCl3): δ = 39.2 (Cq, Ad-C), 47.3 (–, Ad-CH2), 115.6
C-4), 140.5 (C , Ar-C-1Ј), 145.8 (C , Ar-C-1) ppm. IR (ATR): ν =
˜
q
q
3025 (vw), 2922 (vw), 1597 (vw), 1559 (vw), 1484 (w), 1398 (vw),
1264 (vw), 1191 (vw), 1158 (vw), 1120 (vw), 1075 (vw), 1039 (vw),
1006 (w), 911 (vw), 828 (w), 761 (w), 744 (w), 722 (w), 624 (vw),
567 (vw), 541 (vw), 494 (w) cm–1.
1,3,5,7-Tetrakis(4Ј-chloro-[1,1Ј-biphenyl]-4-yl)adamantane (3e): The
reaction was carried out according to general procedure A using (4-
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Eur. J. Org. Chem. 2011, 1743–1754