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Synlett 2015; 26(17): 2429-2433
DOI: 10.1055/s-0035-1560212
DOI: 10.1055/s-0035-1560212
letter
One-Pot Palladium-Catalyzed Synthesis of Benzo[b]carbazolediones
Weitere Informationen
Publikationsverlauf
Received: 24. Juni 2015
Accepted after revision: 09. August 2015
Publikationsdatum:
23. September 2015 (online)
![](https://www.thieme-connect.de/media/synlett/201517/lookinside/thumbnails/st-2015-d0467-l_10-1055_s-0035-1560212-1.jpg)
Abstract
A palladium-catalyzed one-pot reaction for the synthesis of benzo[b]carbazolediones is described which proceeds by amination of 2,3-dibromonaphthoquinone, Suzuki cross-coupling with (2-bromophenyl)boronic acid, and subsequent intramolecular C–N Buchwald–Hartwig cyclization with amines.
Key words
cyclizations - one-pot reaction - Suzuki–Miyaura reaction - Buchwald–Hartwig reaction - palladiumSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560212.
- Supporting Information
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References and Notes
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- 12 General Procedures for the Synthesis of 4a–w 2,3-Dibromo-1,4-naphthoquinone 1 (0.3 mmol), the appropriate amine (0.3 mmol), and H2O (1 mL) were poured into a pressure tube. The reaction was set up at 60 °C for 6 h, then, 2-bromophenylboronic acid (0.3 mmol), Pd(PPh3)4 (5 mol%), Pd2(dba)3 (5 mol%), RuPhos (10 mol%), K3PO4 (0.9 mmol), and 1,4-dioxane (10 mL) were added under argon. The tube was sealed with a Teflon valve and stirred at 90 °C. After 24 h, the mixture was allowed to reach r.t., diluted with H2O, and extracted with CH2Cl2. The combined organic layers were dried over Na2SO4 and concentrated under vacuum. The crude material was purified by flash column chromatography on silica gel. 2-Bromo-3-(p-tolylamino)naphthalene-1,4-dione (2) Dark red solid; mp 157–158 °C. 1H NMR (300 MHz, CDCl3): δ = 8.19 (dd, 3 J = 7.6 Hz, 4 J = 1.3 Hz, 1 H), 8.14–8.05 (m, 1 H), 7.81–7.60 (m, 3 H), 7.15 (d, 3 J = 8.2 Hz, 2 H), 7.00 (d, 3 J = 8.3 Hz, 2 H), 2.36 (s, 3 H, CH3). 13C NMR (75 MHz, CDCl3): δ = 180.3, 177.4 (C=O), 144.4, 136.0 (C), 135.1 (CH), 135.0 (C), 133.0 (CH), 132.6, 130.0 (C), 129.2 (2CH), 127.5, 127.2 (CH), 125.0 (2 CH), 107.0 (C), 21.2 (CH3). IR (ATR): ν = 3302 (m), 3223 (w), 3095 (w), 3024 (w), 2916 (w), 1672 (s), 1645 (m), 1630 (m), 1591 (m), 1581 (m), 1566 (m), 1547 (s), 1516 (m), 1497 (m), 1479 (m), 1454 (m), 1410 (m), 1369 (w), 1329 (m), 1298 (m), 1282 (m), 1263 (s), 1234 (s), 1188 (m), 1174 (m), 1161 (m), 1124 (s), 1111 (s), 1097 (m), 1078 (m), 1043 (m), 1026 (m), 1012 (m), 974 (m), 960 (m), 941 (m), 908 (m), 895 (m), 845 (m), 831 (m), 818 (m), 804 (m), 787 (s), 773 (s), 752 (m), 717 (s), 700 (vs), 679 (s), 660 (m), 636 (m), 625 (s), 604 (m), 542 (s), 530 (m) cm–1. MS (EI, 70 eV): m/z (%) = 341 (73) [M+], 326 (4), 262 (100), 247 (12), 219 (9), 178 (10), 158 (3), 130 (5), 105 (13), 91 (29), 76 (14), 65 (21), 50 (7), 39 (6). HRMS (EI): m/z calcd for C17H12BrNO2 [M+]: 341.00459; found: 341.00382. 2-(2-Bromophenyl)-3-(p-tolylamino)naphthalene-1,4-dione (3) Red solid (21 mg, 17%); mp 175–176 °C. 1H NMR (250 MHz, CDCl3): δ = 8.23–8.11 (m, 2 H), 7.82–7.66 (m, 3 H), 7.27–7.20 (m, 1 H), 7.04–6.81 (m, 3 H), 6.78–6.62 (m, 4 H), 2.14 (s, 3 H, CH3). 13C NMR (63 MHz, CDCl3): δ = 182.9, 181.5 (C=O), 142.2, 135.2 (C), 135.1 (CH), 134.6, 134.3, 133.6 (C), 132.9, 132.4, 132.2 (CH), 130.4 (C), 128.7 (CH), 128.5 (2 CH), 126.9, 126.5, 126.5 (CH), 125.3 (C), 124.6 (2 CH), 115.9 (C), 20.9 (CH3). IR (ATR): ν = 3331 (w), 3298 (s), 3064 (w), 3045 (w), 3010 (w), 2920 (w), 1674 (s), 1633 (m), 1612 (w), 1595 (m), 1569 (s), 1516 (s), 1505 (s), 1469 (s), 1425 (m), 1407 (m), 1379 (w), 1328 (s), 1294 (s), 1279 (s), 1253 (s), 1211 (m), 1173 (m), 1156 (m), 1133 (m), 1106 (s), 1052 (m), 1040 (m), 1029 (m), 1018 (s), 1006 (s), 966 (m), 942 (m), 920 (m), 863 (m), 850 (m), 835 (m), 811 (s), 795 (s), 748 (vs), 727 (s), 714 (vs), 670 (s), 655 (s), 647 (s), 632 (s), 599 (s), 578 (s), 530.5 (s) cm–1. MS (EI, 70 eV): m/z (%) = 419 (4), 417 (5) [M+], 339 (27), 338 (100), 324 (7), 323 (26), 295 (3) 294 (5), 281 (2), 266 (2), 239 (2), 221 (1), 204 (2), 190 (6), 176 (7), 169 (3), 165 (6), 161 (9), 147 (2), 139 (1), 104 (3), 91 (4), 76 (5), 65 (4), 51 (1), 39 (2). HRMS (EI): m/z calcd for C23H16BrNO2 [M+]: 417.03589; found: 417.03524; m/z calcd for C23H16 81BrNO2 [M+]: 419.03385; found: 419.03478. 5-(p-Tolyl)-5H-benzo[b]carbazole-6,11-dione (4b) Orange solid (48 mg, 49%); mp 266–268 °C. 1H NMR (250 MHz, CDCl3): δ = 8.56–8.46 (m, 1 H), 8.30–8.19 (m, 1 H), 8.10–7.96 (m, 1 H), 7.79–7.58 (m, 2 H), 7.46–7.29 (m, 6 H), 7.21–7.09 (m, 1 H), 2.52 (s, 3 H, CH3). 13C NMR (63 MHz, CDCl3): δ = 181.7, 177.7 (C=O), 141.3, 139.4, 135.7, 134.3 (C), 134.2 (C), 133.8 (CH), 133.7 (C), 133.1 (CH), 130.3 (2 CH), 127.7 (CH), 127.4 (2 CH), 126.6 (CH), 126.4 (CH), 124.9 (CH), 124.0 (C), 123.8 (CH),119.9 (C), 112.3 (CH), 21.5 (CH3). IR (ATR): ν = 3062 (w), 3050 (w), 2956 (w), 2921 (m), 2851 (m), 1732 (w), 1660 (m), 1641 (m), 1612 (w), 1588 (m), 1516 (s), 1488 (m), 1458 (s), 1418 (m), 1401 (m), 1350 (w), 1318 (m), 1310 (w), 1282 (m), 1158 (m), 1149 (m), 1131 (m), 1111 (m), 1095 (m), 1045 (s), 1017 (s), 1003 (s), 971 (m), 961.3 (m), 947 (m), 937 (m), 894 (m), 877 (m), 847 (m), 832 (s), 799 (s), 790 (s), 744 (vs), 725 (m), 709 (s), 697 (s), 664 (m), 648 (m), 640 (m), 610 (m), 596 (s), 571 (m) cm–1. MS (EI, 70 eV): m/z (%) = 337 (100) [M+], 322 (38), 308 (9), 278 (12), 252 (2), 239 (1), 204 (1), 190 (3), 176 (1), 168 (11), 163 (5), 152 (2), 147 (2), 139 (4), 132 (7), 126 (2), 113 (1), 91 (2), 76 (2), 65 (3), 51 (1), 39 (2). HRMS (EI): m/z calcd for C23H15NO2 [M+]: 337.10973; found: 337.10925.
- 13 CCDC 1002799 contains all crystallographic details of this publication and is available free of charge at www.ccdc.cam.ac.uk/ conts/retrieving.html or can be ordered from the following address: Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: +44(1223)336033; or deposit@ccdc.cam.ac.uk