One-Pot Palladium-Catalyzed Synthesis of Benzo[b]carbazolediones

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 - palladium

• 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: [phone]; or [e-mail]