10.1002/ejoc.201801232
European Journal of Organic Chemistry
FULL PAPER
reacted in dioxane-water mixture (2/1, 60 mL) for 72h according to general
procedure F. The crude product was purified by column chromatography
(n-hexane) to give (14) (0.994 g, 37 %) as a white solid. 1H-NMR (500 MHz,
CDCl3): = 7.47 (s, 2H, CHAr), 7.32 (s, 4H, CHAr), 7.15 (s, 2H, CHAr), 2.41
(s, 6H, ArCH3), 2.27 (s, 6H, ArCH3) ppm. 13C-NMR (125 MHz, CDCl3): =
140.9 (CIV), 139.8 (CIV), 135.2 (CIV), 134.8 (CIV), 134.0 (CHAr), 132.2 (CHAr),
129.0 (CHAr), 123.7 (CIV), 22.4 (ArCH3), 19.9 (ArCH3) ppm. IR (ATR): =
2954, 2919, 2855, 1475, 1442, 1373, 1357, 1177, 1113 cm-1. MS (EI): m/z
= 446 (4) – 444 (9) – 442 (4) [M+]. HRMS (EI): m/z C22H20Br2, calcd.:
441.9932, found: 441.9930.
reacted in dioxane-water mixture (2/1, 60 mL) for 72h according to general
procedure C. The crude product was purified by column chromatography
(30 to 50 % dichloromethane in n-hexane) to give (19) (0.919 g, 75 %) as
a pale yellow solid. 1H-NMR (500 MHz, CDCl3): = 8.08 (d, 2H, J = 8.5 Hz,
CHAr), 7.46 (s, 1H, CHAr), 7.36 (d, 2H, J = 8.5 Hz, CHAr), 7.08 (s, 1H, CHAr),
3.95 (s, 3H, CO2CH3), 2.39 (s, 3H, ArCH3), 2.20 (s, 3H, ArCH3) ppm. 13C-
NMR (125 MHz, CDCl3): = 167.1 (CO2CH3), 145.8 (CIVAr), 140.1 (CIVAr),
135.4 (CIVAr), 134.6 (CIVAr), 134.1 (CHAr), 131.8 (CHAr), 129.6 (CHAr), 129.2
(CHAr), 124.3 (CIVAr), 52.3 (CO2CH3), 22.4 (ArCH3), 19.8 (ArCH3) ppm. IR
(ATR): = 2949, 1717, 1602, 1484, 1433, 1382, 1271 cm-1. MS (EI): m/z
= 320 (100) – 318 (83) [M+], 289 (40) – 287 (37) [M+-OCH3], 240 (56) [M+-
Br]. HRMS (EI): m/z C16H15BrO2, calcd.: 318.0255, found: 318.0258.
Diisopropyl
2',2''',5',5'''-tetramethyl-[1,1':4',1'':4'',1''':4''',1''''-
(16): 4,4''-dibromo-2,2'',5,5''-
quinquephenyl]-4,4''''-dicarboxylate
tetramethyl-1,1':4',1''-terphenyl (14) (0.300 g, 0.68 mmol, 1 equiv), 4-
isopropoxycarbonylphenylboronic acid (15) (0.843 g, 4.05 mmol, 6 equiv),
Pd(PPh3)4 (78 mg, 0.07 mmol, 0.1 equiv) and Na2CO3 (1.002 g, 9.46 mmol,
14 equiv) were reacted in toluene-dioxane-water mixture (2/2/1, 100 mL)
for 72h according to general procedure D. The crude product was purified
by column chromatography (40 to 70 % dichloromethane in n-hexane) to
give (16) (0.294 g, 71 %) as a white solid. 1H-NMR (500 MHz, CDCl3): =
8.12 (d, 4H, J = 8.0 Hz, CHAr), 7.47 (d, 4H, J = 8.0 Hz, CHAr), 7.44 (s, 4H,
CHAr), 7.25 (s, 2H, CHAr), 7.18 (s, 2H, CHAr), 5.30 (sep, 2H, J = 6.5 Hz,
CH(CH3)2), 2.37 (s, 6H, ArCH3), 2.30 (s, 6H, ArCH3), 1.41 (d, 12H, J =
6.5 Hz, CH(CH3)2) ppm. 13C-NMR (125 MHz, CDCl3): = 166.2 (CO2iPr),
146.4 (CIV), 141.3 (CIV), 140.2 (CIV), 140.1 (CIV), 133.0 (CIV), 132.7 (CIV),
132.2 (CHAr), 131.8 (CHAr), 129.5 (CHAr), 129.4 (CHAr), 129.1 (CHAr), 68.5
(CH(CH3)2), 22.2 (CH(CH3)2), 20.2 (ArCH3), 20.0 (ArCH3) ppm. IR (ATR):
= 2984, 1710, 1608, 1485, 1376, 1272, 1177 cm-1. MS (EI): m/z = 610
(54) [M+]. HRMS (EI): m/z C42H42O4, calcd.: 610.3083, found: 610.3080.
EA (C42H42O4): Calcd.: C, 82.59 %; H, 6.93 %, found: C, 82.19 %; H,
6.85 %.
Methyl
2',5'-dimethyl-4'-(pinacolatoboronyl)-[1,1'-biphenyl]-4-
carboxylate (20): Methyl 4'-bromo-2',5'-dimethyl-[1,1'-biphenyl]-4-
carboxylate (19) (0.900 g, 2.82 mmol, 1 equiv), B2pin2 (2) (0.788 g,
3.10 mmol, 1.1 equiv), Pd(dppf)Cl2 (115 mg, 0.14 mmol, 0.05 equiv), and
AcOK (0.830 g, 8.46 mmol, 3 equiv) were reacted in DMSO (30 mL) for
18h according to general procedure A. The crude product was purified
by column chromatography (30 to 70 % dichloromethane in n-hexane) to
give (20) (0.575 g, 56 %) as a pale yellow solid. 1H-NMR (500 MHz,
CDCl3): = 8.07 (d, 2H, J = 8.0 Hz, CHAr), 7.68 (s, 1H, CHAr), 7.39 (d, 2H,
J = 8.0 Hz, CHAr), 7.05 (s, 1H, CHAr), 3.94 (s, 3H, CO2CH3), 2.54 and 2.23
(2 s, 6H, ArCH3), 1.36 (s, 12H, CH3(Bpin)). 13C-NMR (125 MHz, CDCl3): =
167.2 (CO2CH3), 146.9 (CIV), 143.3 (CIV), 142.5 (CIV), 138.2 (CHAr), 131.4
(CIV), 131.1 (CHAr), 129.5 and 129.3 (CHAr), 83.6 (CIV(Bpin)), 52.3 (CO2CH3),
25.0 (CH3(Bpin)), 21.8 and 19.7 (ArCH3) ppm. IR (ATR): = 2977, 2927,
1720, 1606, 1437, 1410, 1390, 1377, 1279, 1178 cm-1. MS (EI): m/z = 366
(100) [M+], 351 (10) [M+-CH3]. HRMS (EI): m/z C22H27BO4, calcd.:
366.2002, found: 366.2001.
Dimethyl
[1,1':4',1'':4'',1''':4''',1'''':4'''',1''''':4''''',1''''''-septephenyl]-4,4''''''-
dicarboxylate (21): 4,4''-dibromo-2,2'',5,5''-tetramethyl-1,1':4',1''-
2',2'',2'''',2''''',5',5'',5'''',5'''''-octamethyl-
2',2''',5',5'''-tetramethyl-[1,1':4',1'':4'',1''':4''',1''''-quinquephenyl]-4,4''''-
dicarboxylic
acid
(17):
Diisopropyl
2',2''',5',5'''-tetramethyl-
[1,1':4',1'':4'',1''':4''',1''''-quinquephenyl]-4,4''''-dicarboxylate (16) (0.200 g,
0.33 mmol, 1 equiv) and NaOH (0.786 g, 19.65 mmol, 60 equiv) were
reacted in MeOH-H2O (10/1, 33 mL) for 24h according to general
procedure J to give (17) (0.150 g, 87 %) as a white solid. 1H-NMR
(600 MHz, DMSO): = 8.02 (b-d, 6H, J = 6.6 Hz, CHAr and CO2H), 7.82
(d, 2H, J = 6.6 Hz, CHAr), 7.51 (d, 2H, J = 6.6 Hz, CHAr), 7.49 (s, 4H, CHAr),
7.25 (s, 2H, CHAr), 7.21 (s, 2H, CHAr), 2.32 (s, 6H, ArCH3), 2.27 (s, 6H,
ArCH3) ppm. 13C-NMR (150 MHz, DMSO): = 161.3, 142.8, 140.3, 139.5,
132.3, 132.1, 131.7, 131.4, 129.9, 129.1, 129.0, 128.8, 126.8, 19.6,
19.5 ppm. MS (EI): m/z = 526 (100) [M+]. HRMS (EI): m/z C36H30O4, calcd.:
526.2144, found: 526.2142.
terphenyl (14) (0.300 g, 0.68 mmol, 1 equiv), methyl 2',5'-dimethyl-4'-
(pinacolatoboronyl)-[1,1'-biphenyl]-4-carboxylate (20) (0.742 g, 2.03 mmol,
3 equiv), Pd(dppf)Cl2 (55 mg, 0.07 mmol, 0.1 equiv), and CsF (0.616 g,
4.05 mmol, 6 equiv) were reacted in dioxane-water mixture (2/1, 60 mL)
for 60h according to general procedure E. The crude product was purified
by column chromatography (0 to 70 % dichloromethane in n-hexane) to
give (21) (0.456 g, 89 %) as a white solid. 1H-NMR (500 MHz, CDCl3): =
8.12 (d, 4H, J = 8.0 Hz, CHAr), 7.49 (d, 4H, J = 8.0 Hz, CHAr), 7.47 (s, 4H,
CHAr), 7.24 (s, 2H, CHAr), 7.16 (s, 2H, CHAr), 7.11 (s, 2H, CHAr), 7.09 (s,
2H, CHAr), 3.96 (s, 6H, CO2CH3), 2.37 and 2.28 (2 s, 12H, ArCH3), 2.16 (s,
12H, ArCH3) ppm. 13C-NMR (125 MHz, CDCl3): = 167.3 (CO2), 146.9
(CIV), 141.2 (CIV), 140.6 (CIV), 140.4 (CIV), 140.3 (CIV), 139.7 (CIV), 133.6
(CIV), 133.3 (CIV), 132.5 (CIV), 132.3 (CIV), 131.8 (CHAr), 131.6 (CHAr),
131.5 (CHAr), 131.1 (CHAr), 129.6 (CHAr), 129.5 (CHAr), 129.1 (CHAr), 128.6
(CIV), 52.3 (CO2CH3), 20.3 (ArCH3), 20.1 (ArCH3), 19.6 (ArCH3) ppm. IR
(ATR): = 3006, 2951, 2918, 1723, 1608, 1483, 1437, 1275, 1178,
1114 cm-1. MS (EI): m/z = 762 (74) [M+]. HRMS (EI): m/z C54H50O4, calcd.:
762.3709, found: 762.3707.
Methyl 4-(pinacolatoboronyl)benzoate (18): Methyl 4-bromobenzoate
(0.500 g, 2.33 mmol, 1 equiv), B2pin2 (2) (0.649 g, 2.56 mmol, 1.1 equiv),
Pd(dppf)Cl2 (0.095 g, 0.12 mmol, 0.05 equiv), and AcOK (0.685 g,
6.98 mmol, 3 equiv) were reacted in DMSO (15 mL) for 72h according to
general procedure A. The crude product was purified by column
chromatography (0 to 5% ethyl acetate in n-hexane) to give (18) (0.505 g,
83 %) as a pale grey solid. 1H-NMR (500 MHz, CDCl3): = 8.02 (d, 2H, J
= 8.0 Hz, CHAr), 7.87 (d, 2H, J = 8.0 Hz, CHAr), 3.92 (s, 3H, CO2CH3), 1.35
(s, 12H, CH3(Bpin)) ppm. 13C-NMR (125 MHz, CDCl3): = 167.3 (CO2Me),
134.8 (CHAr), 132.4 (CIV), 128.7 (CHAr), 84.3 (CIV(Bpin)), 52.3 (CO2CH3),
25.0 (CH3(Bpin)) ppm. IR (ATR): = 2985, 2924, 1720, 1614, 1561, 1508,
1434, 1397, 1326, 1190 cm-1. MS (EI): m/z = 262 (38) [M+], 247 (67) [M+-
CH3]. HRMS (EI): m/z C14H19BO4, calcd.: 262.1376, found: 262.1376.
2',2'',2'''',2''''',5',5'',5'''',5'''''-octamethyl-
[1,1':4',1'':4'',1''':4''',1'''':4'''',1''''':4''''',1''''''-septephenyl]-4,4''''''-
dicarboxylic acid (22): Dimethyl 2',2'',2'''',2''''',5',5'',5'''',5'''''-octamethyl-
[1,1':4',1'':4'',1''':4''',1'''':4'''',1''''':4''''',1''''''-septephenyl]-4,4''''''-dicarboxylate
(21) (0.250 g, 0.33 mmol, 1 equiv) and NaOH (0.786 g, 19.66 mmol,
60 equiv) were reacted in MeOH-H2O (10/1, 33 mL) for 24h according to
general procedure J to give (22) (0.205 g, 85 %) as a white solid. 1H-
NMR (500 MHz, DMSO): = 12.96 (br-s, 2H, CO2H), 8.03 (br-s, 4H, CHAr),
7.55 (br-s, 4H, CHAr), 7.51 (s, 4H, CHAr), 7.25 (s, 2H, CHAr), 7.21 (s, 2H,
CHAr), 7. 09 (s, 4H, CHAr), 2.32 and 2.25 (2 s, 12H, ArCH3), 2.10 (s, 12H,
ArCH3) ppm. MS (EI): m/z = 734 (23) [M+].
Methyl 4'-bromo-2',5'-dimethyl-[1,1'-biphenyl]-4-carboxylate (19):
Methyl 4-(pinacolatoboronyl)benzoate (18) (1.000 g, 3.82 mmol, 1 equiv),
2,5-dibromo-p-xylene (9) (5.035 g, 19.08 mmol, 5 equiv), Pd(dppf)Cl2 (156
mg, 0.19 mmol, 0.05 equiv), and CsF (1.739 g, 11.45 mmol, 3 equiv) were
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