O. A. Akrawi et al. / Tetrahedron Letters 52 (2011) 1093–1095
1095
were separated and the latter was extracted with EtOAc (2 Â 25 mL). The
combined organic layers were dried (Na2SO4), filtered and the filtrate was
concentrated in vacuo. The residue was purified by column chromatography
1165, 1094, 1062, 1050, 1018, 959, 927, 900, 834 (w), 818 (s), 798, 739 (m), 710
(s), 664, 645, 615, 5191, 549 (w) cmÀ1. GC–MS (EI, 70 eV): m/z (%) = 416 ([M]+,
36), 415 ([MÀH]+, 45), 400 (09), 387 (100), 372 (10). HRMS (EI, 70 eV): calcd for
(EtOAc/heptanes) to give 3 as a yellow solid (1.37 g, 57%). Mp: 173–175 °C. 1
H
C
30H23O2 [MÀH]+: 415.16926; found: 415.168812.
NMR (300 MHz, DMSO-d6): d = 6.56 (d, 1H, J = 2.4 Hz, ArH), 7.08 (d, 1H,
J = 2.4 Hz, ArH), 7.83–7.91 (m, 2H, ArH), 8.08–8.15 (m, 2H, ArH), 11.29 (s, 1H,
ArOH), 12.69 (s, 1H, ArOH). 13C NMR (75.5 MHz, DMSO-d6): d = 106.7 (C), 107.6,
108.3, 125.4, 125.8 (CH), 131.9, 132, (C), 133.5, 133.7 (CH), 133.9, 163.8, 164.4
(C), 180.8, 184.9 (CO). IR (KBr): v = 3368 (m), 3070, 2921, 2854, 1743, 1722,
1711, 1670 (w), 1634, 1587 (m), 1547, 1537, 1512, 1485, 1485 (w), 1452, 1413
(m), 1379 (w), 1336, 1303, 1287, 1258, 1191, 1171, 1155 (m), 1094, 1061, 1029
(w), 1006 (m), 980, 923, 876 (w), 861, 799, 778 (m), 733 (w), 725 (m), 711 (s),
653, 640, 600, 547 (m) cm-1. MS (EI, 70 eV): m/z (%) = 240 ([M]+, 100), 212 (13),
12. General procedure B for the synthesis of 7a–f: A 1,4-dioxane solution of 4
(0.2 mmol), arylboronic acid (1.0 equiv), K3PO4 (1.5 equiv) and Pd(PPh3)4
(3 mol %) was heated at 60 °C for 30 h under argon atmosphere. After cooling
to 20 °C, CH2Cl2 (20 mL) was added, the solution was filtered, and the filtrate
was concentrated in vacuo. The residue was purified by column
chromatography (EtOAc/heptanes).
13. 4-(3-Chlorophenyl)-9,10-dioxo-9,10-dihydroanthracen-2-yl trifluoromethanesul-
fonate (7f): Starting with 4 (100 mg, 0.2 mmol), 7f was prepared as a yellow
solid (63 mg, 68%). Mp: 134–136 °C. Reaction temperature: 60 °C for 30 h. 1H
NMR (300 MHz, CDCl3): d = 7.11 (dt, 1H, J = 1.7, 7.1 Hz, ArH), 7.21–7.22 (m, 1H,
ArH), 7.31–7.39 (m, 3H, ArH), 7.69–7.77 (m, 2H, ArH), 8.02–8.08 (m, 1H, ArH).
8.19–8.26 (m, 2H, ArH). 13C NMR (62.9 MHz, CDCl3): d = 117.7 (q, JC,F = 320.3,
CF3), 120.0, 126.1, 127.2, 127.7, 127.9, 128.2, 129.6, 129.7 (CH), 130.5, 132.3,
134.1, 134.2 (C), 134.3, 135.0 (CH), 137.4, 141.6, 146.2, 151.6 (C), 181.3, 181.7
(CO). IR (KBr): v = 3072, 2917, 2849 (w), 1672 (s), 1577, 1567, 1478, 1423, 1320
(m), 1297 (w), 1271, 1244 (m), 1210 (s), 1164 (w), 1134 (s), 1101, 1086, 1078
(m), 1037, 1002, 979 (w), 931 (s), 911, 879, 845, 827, 816, 801, 785 (m), 767,
741 (w), 724, 708, 692, 658, 644, 628 (m), 606, 589 (s), 565 (m) cmÀ1. GC–MS
(EI, 70 eV): m/z (%) = 468 ([M, 37Cl]+, 36), 466 ([M, 35Cl]+, 99), 431 (89), 298 (33),
270 (100), 213 (62). HRMS (EI, 70 eV): calcd. for C21H10ClO5F3S [M, 35Cl]+:
465.98841; found: 465.987174.
14. General procedure C for the synthesis of 8a,b: A 1,4-dioxane solution of 4
(0.3 mmol), Ar1B(OH)2 (1.0 equiv), K3PO4, (3.0 equiv) and Pd(PPh3)4 (3 mol %)
was heated at 60 °C for 30 h under argon atmosphere. After cooling to 20 °C,
Ar2B(OH)2 (1.2 equiv), Pd(PPh3)4 (3 mol %) were added and reaction mixture
was heated at 100 °C for a further 5 h. The reaction mixture was cooled again to
20 °C, H2O was added, and the reaction mixture was extracted with CH2Cl2
(25 Â 3 mL). The organic layers were dried (Na2SO4), filtered, and then
concentrated in vacuo. The residue was purified by column chromatography
(EtOAc/heptanes).
184 (19), 155 (13), 127 (17). HRMS (EI, 70 eV): calcd for
240.04226; found: 240.042311.
C
14H8O4 [M]+:
9. Synthesis
of
9,10-dioxo-9,10-dihydroanthracene-1,3-diyl
bis(trifluoromethanesulfonate) (4): To a CH2Cl2 (50 mL) solution of 3 (1.2 g,
5.0 mmol), pyridine (1.6 mL, 20 mmol) and Tf2O (2.1 mL, 12 mmol) were added
and the reaction mixture was stirred at 20 °C under argon atmosphere for 8 h.
To the reaction mixture toluene (5 mL) was added and the solution was
concentrated in vacuo. The residue was purified by chromatography (EtOAc/
heptanes) without aqueous work up to yield 4 as a light yellow solid (1.97 g,
78%). Mp: 164–166 °C. 1H NMR (300 MHz, CDCl3): d = 7.46 (d, 1H, J = 2.5 Hz,
ArH), 7.77–7.86 (m, 2H, ArH), 8.22–8.33 (m, 3H, ArH). 19F NMR (282.4 MHz,
CDCl3): d = À73.1, À72.2. 13C NMR (62.9 MHz, CDCl3): d = 118.6 (q, JC,F = 320.8,
CF3), 118.7 (q, JC,F = 320.8, CF3), 120.7, 122.0 (CH), 125.5 (C), 127.5, 128.1 (CH),
131.2, 133.5 (C), 135.0, 135.5 (CH), 137.5, 148.7, 152.2 (C), 179.6, 179.7 (CO). IR
(KBr): v = 3096, 3067, 2961, 2931, 2861 (w), 1677 (s), 1664, 1601 (w), 1586
(m), 1432 (s), 1331, 1316 (w), 1304, 1286 (m), 1256 (w), 1245 (m), 1203 (s),
1158 (w), 1132 (s), 1104 (m), 1046, 1015 (w), 991 (m), 937, 918 (w), 903, 869,
819, 795, 768, 757, 743, 732, 713 (m), 673, 651, 617 (w), 604, 591, 575 (m), 541
(w) cmÀ1. GC–MS (EI, 70 eV): m/z (%) = 504 ([M]+, 100), 440 (09), 375 (22), 279
(82), 251 (49). HRMS (EI, 70 eV): calcd. for C16H6F6O8S2 [M]+: 503.94083;
found: 503.94066.
10. General procedure A for the synthesis of 6a–h: A 1,4-dioxane solution of 9,10-
15. 1-(3-Chlorophenyl)-3-(p-tolyl)anthracene-9,10-dione (8b): Starting with 4
dioxo-9,10-dihydroanthracene-1,3-diyl
bis(trifluoromethanesulfonate)
4
(150 mg, 0.3 mmol), 3-chlorophenylboronic acid (Ar1B(OH)2) (47 mg,
0.30 mmol), K3PO4 (191 mg, 0.9 mmol), Pd(PPh3)4 (21 mg, 6 mol %), and p-
tolylboronic acid (Ar2B(OH)2) (49 mg, 0.30 mmol), 8b was prepared as a yellow
solid (91 mg, 74%). Mp: 191–193. Reaction temperature: 60 °C for 30 h, then
100 °C for 5 h. 1H NMR (300 MHz, CDCl3): d = 2.33 (s, 3H, CH3), 7.12–7.33 (m,
6H, ArH), 7.55 (d, 2H, J = 8.1 Hz, ArH), 7.65–7.68 (m, 3H, ArH), 8.03–8.06 (m,
1H, ArH), 8.20–8.23 (m, 1H, ArH), 8.54 (d, 1H, J = 1.9 Hz, ArH). 13C NMR
(62.9 MHz, CDCl3): d = 21.2 (CH3), 125.5, 126.4, 126.9, 127.1, 127.2, 127.4,
128.1 (CH), 129.1 (C), 129.3, 129.9 (CH), 132.9 (C), 133.7 (CH), 133.9 (C), 134.3
(CH), 134.5 (C), 135.2 (CH), 135.3, 139.3, 143.5, 143.9, 145.5 (C), 182.8, 183.3
(CO). IR (KBr): v = 3063, 3034, 2950, 2915, 2852 (w), 1667 (s), 1613 (w), 1587,
1564, 1557 (m), 1537, 1518, 1504, 1476, 1445, 1408, 1386 (w), 1337, 1304,
1294, 1269, 1226, 1194, 1188, 1168 (m), 1153, 1077, 1061, 1034, 1018, 998
(w), 966, 930, 917, 901, 865, 853, 814, 785, 738 (m), 714, 713 (s), 689, 661 (m),
650, 628, 619, 597, 567, 538 (w) cmÀ1. GC–MS (EI, 70 eV): m/z (%) = 410 ([M,
37Cl]+, 21), 408 ([M, 35Cl]+, 58), 407 ([MÀH]+, 100), 373 (27). HRMS (EI, 70 eV):
calcd for C27H16O2Cl [MÀH]+: 407.08333; found: 407.082634.
(0.2 mmol), arylboronic acid (2.4 equiv), K3PO4 (3.0 equiv) and Pd(PPh3)4
(6 mol %) was heated at 100 °C for 7 h under argon atmosphere. After cooling
to 20 °C, H2O was added and the reaction mixture was extracted with CH2Cl2
(25 Â 3 mL). The organic layers were dried (Na2SO4), filtered, and concentrated
in vacuo. The residue was purified by column chromatography (EtOAc/
heptanes).
11. 1,3-Bis(4-ethylphenyl)anthracene-9,10-dione (6b): Starting with
4 (100 mg,
0.2 mmol), arylboronic acid (72 mg, 0.48 mmol), K3PO4 (127 mg, 0.6 mmol),
and Pd(PPh3)4 (14 mg, 6 mol %), 6b was prepared as a yellow solid (73 mg,
88%). Mp: 167–169 °C. Reaction temperature: 100 °C for 7 h. 1H NMR
(250 MHz, CDCl3): d = 1.17 (t, 3H, J = 7.6 Hz, CH3), 1.24 (t, 3H, J = 7.6 Hz, CH3),
2.60 (q, 2H, J = 7.6 Hz, CH2), 2.67 (q, 2H, J = 7.7 Hz, CH2), 7.13–7.22 (m, 6H, ArH),
7.56 (d, 2H, J = 8.3 Hz, ArH), 7.60–7.64 (m, 2H, ArH), 7.71 (d, 1H, J = 2.1 Hz,
ArH), 8.02–8.06 (m, 1H, ArH), 8.16-8.20 (m, 1H, ArH), 8.50 (d, 1H, J = 2.1 Hz,
CH2). 13C NMR (62.9 MHz, CDCl3): d = 14.3, 14.4 (CH3), 14.3, 14.4 (CH3), 27.5,
27.6 (CH2), 123.9, 125.7, 126.1, 126.3, 126.5, 127.1, 127.6 (CH), 128.2, 131.9 (C),
132.4, 133.1 (CH), 133.7, 134.3 (C), 134.7 (CH), 138.3, 142.1, 144.1 (C), 182.0,
182.4 (CO). IR (KBr): v = 3054, 3025, 2960, 2929, 2869 (w), 1668, 1588, 1580
(m), 1556, 1513, 1453, 1427, 1410, 1386 (w), 1340, 1307 (m), 1270 (s), 1186,
16. For a simple guide for the prediction of the site-selectivity of palladium(0)
catalyzed cross-coupling reactions based on the 1H NMR chemical shift values,
see: Handy, S. T.; Zhang, Y. Chem. Commun. 2006, 299.