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Synlett 2015; 26(11): 1549-1552
DOI: 10.1055/s-0034-1380713
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© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Approach to Malasseziazole A and First Total Synthesis of Malasseziazole C

Ute Kober
Department Chemie, Technische Universität Dresden, Bergstr. 66, 01069 Dresden, Germany   Email: hans-joachim.knoelker@tu-dresden.de
,
Hans-Joachim Knölker*
Department Chemie, Technische Universität Dresden, Bergstr. 66, 01069 Dresden, Germany   Email: hans-joachim.knoelker@tu-dresden.de
› Author Affiliations
Further Information

Publication History

Received: 07 March 2015

Accepted after revision: 14 April 2015

Publication Date:
30 April 2015 (online)

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Dedicated to Professor K. Peter C. Vollhardt on the occasion of his 69th birthday

Abstract

We describe a convergent route to 5,11-dihydroindolo[3,2-b]carbazoles using a twofold oxidative cyclization as key step. The method has been applied to the synthesis of a precursor for malasseziazole A and to the first total synthesis of malasseziazole C.

Key words

alkaloids - catalysis - cyclization - indolocarbazoles - natural products - palladium

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380713.
  • Supporting Information
 

  • References and Notes

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  • 20 6-Acetyl-5,11-dihydro-indolo[3,2-b]carbazole (10) Yellow solid; mp 244 °C. UV (MeOH): λ = 213 (sh), 223, 254, 306, 338 (sh), 357, 438 nm. Fluorescence (MeOH): λex = 223 nm, λem = 507 nm. IR (ATR): ν = 3456, 3400, 3051, 2920, 2851, 1640, 1605, 1558, 1512, 1457, 1418, 1353, 1320, 1292, 1270, 1221, 1186, 1168, 1144, 1109, 1010, 988, 961, 934, 866, 739, 692, 641, 621 cm–1. 1H NMR (600 MHz, CDCl3): δ = 2.96 (s, 3 H), 7.23–7.28 (m, 2 H), 7.46–7.49 (m, 3 H), 7.51–7.52 (m, 1 H), 8.10 (d, J = 7.8 Hz, 1 H), 8.17 (d, J = 8.1 Hz, 1 H), 8.22 (s, 1 H), 8.28 (br s, 1 H), 9.72 (br s, 1 H). 13C NMR and DEPT (150 MHz, CDCl3): δ = 30.93 (CH3), 106.42 (CH), 110.95 (CH), 111.00 (CH), 115.07 (C), 119.26 (CH), 119.46 (CH), 120.26 (C), 120.31 (CH), 121.90 (C), 122.37 (C), 124.08 (CH), 124.25 (C), 126.40 (CH), 126.73 (CH), 135.09 (C), 135.29 (C), 141.15 (2 C), 202.85 (C=O). MS (EI): m/z = 298 (100), 283 (30), 255 (64), 254 (10), 253 (11), 227 (11).
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  • 28 Malasseziazole C (12-Formyl-5,11-dihydroindolo[3,2-b]carbazole-6-carboxylic Acid) (3) Brownish solid; mp >300 °C (decomp.). UV (MeOH): λ = 213, 247, 272 (sh), 307 (sh), 391, 465 nm. Fluorescence (MeOH): λex = 307 nm, λem = 455 nm. IR (ATR): ν = 3448, 3055, 2922, 2852, 1712, 1611, 1585, 1512, 1458, 1392, 1347, 1321, 1299, 1263, 1205, 1158, 1126, 1077, 1022, 954, 895, 839, 804, 741, 698, 653 cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 7.22 (m, 2 H), 7.48 (t, J = 7.6 Hz, 1 H), 7.52 (t, J = 7.7 Hz, 1 H), 7.79 (d, J = 8.2 Hz, 1 H), 7.82 (d, J = 8.1 Hz, 1 H), 8.58 (d, J = 8.2 Hz, 1 H), 8.61 (d, J = 8.1 Hz, 1 H), 11.41 (s, 1 H), 11.44 (s, 1 H), 11.96 (s, 1 H), 13.72 (br s, 1 H). 1H NMR (600 MHz, CD3OD): δ = 7.11–7.13 (m, 1 H), 7.19–7.21 (m, 1 H), 7.40–7.45 (m, 2 H), 7.60 (d, J = 8.0 Hz, 1 H), 7.61 (d, J = 7.9 Hz, 1 H), 8.33 (d, J = 8.0 Hz, 1 H), 8.91 (d, J = 8.2 Hz, 1 H), 11.50 (br s, 1 H). 13C NMR and DEPT (125 MHz, DMSO-d 6): δ = 112.60 (CH), 112.72 (CH), 114.57 (C), 114.93 (C), 119.56 (CH), 119.77 (CH), 120.36 (C), 120.62 (C), 121.15 (C), 123.31 (C), 124.42 (CH), 125.09 (CH), 127.18 (CH), 127.51 (CH), 134.33 (C), 135.39 (C), 142.38 (C), 142.70 (C), 168.57 (C=O), 191.11 (CHO). ESI-MS (+25 V): m/z = 329.1 [M + H]+.
  • 29 5,11-Dihydroindolo[3,2-b]carbazole-6,12-dicarboxylic Acid (17) Red solid; mp >294 °C (decomp.). UV (MeOH): λ = 211, 275 (sh), 294, 366 nm. Fluorescence (MeOH): λex = 294 nm, λem = 515 nm. IR (ATR): ν = 3448, 3413, 2920, 2850, 2577, 1642, 1610, 1570, 1543, 1501, 1473, 1457, 1429, 1314, 1297, 1229, 1207, 1151, 1112, 1021, 891, 857, 793, 763, 746, 699, 624 cm–1. 1H NMR (500 MHz, DMSO-d 6): δ = 7.16 (m, 2 H), 7.45 (m, 2 H), 7.75 (d, J = 8.1 Hz, 2 H), 8.67 (d, J = 8.2 Hz, 2 H), 11.25 (s, 2 H), 13.95 (br s, 2 H). 13C NMR and DEPT (125 MHz, DMSO-d 6): δ = 110.44 (2 C), 111.63 (2 CH), 118.31 (2 CH), 120.35 (2 C), 120.63 (2 C), 124.28 (2 CH), 126.57 (2 CH), 134.72 (2 C), 141.81 (2 C), 168.47 (2 C=O). ESI-MS (+10 V): m/z = 345.2 [M + H]+.