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Synlett 2009(15): 2483-2486  
DOI: 10.1055/s-0029-1217815
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Total Synthesis of New Lipocarbazoles Isolated from the Actinomycete ­Tsukamurella pseudospumae Acta 1857 [¹]

Anne Hänchen, Roderich D. Süssmuth*
Fakultät II - Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 124, 10623 Berlin, Germany
Fax: +49(30)31479651; e-Mail: suessmuth@chem.tu-berlin.de;
Further Information

Publication History

Received 19 May 2009
Publication Date:
17 August 2009 (online)

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Abstract

New lipocarbazoles were synthesized by a sequence of three palladium-mediated coupling reactions and an improved protecting group strategy.

Key words

heterocycles - cross-coupling - total synthesis - hydro­boration - natural products

1

Article 50 in the series ‘Biosynthetic Capacities of Actinomycetes’.

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1

Article 50 in the series ‘Biosynthetic Capacities of Actinomycetes’.

3

Schneider, K.; Nachtigall, J.; Hänchen, A.; Nicholson, G.; Goodfellow, M.; Süssmuth, R. D.; Fiedler, H.-P. J. Nat. Prod. 2009, submitted.

23

Spectral Data for Lipocarbazole A4 (1a)
IR (neat): ν = 3466, 3388, 2920, 2849, 1500, 1466, 1436, 1311, 1233, 1147, 1064, 830, 772, 738 cm-¹. ¹H NMR (400 MHz, DMSO-d 6): δ = 10.65 (s, 1 H), 8.78 (s, 1 H), 7.87-7.85 (d, J = 8.0 Hz, 1 H), 7.41-7.39 (d, J = 8.0 Hz, 1 H), 7.28-7.24 (t, J = 8.0 Hz, 1 H), 7.26 (s, 1 H), 7.04-7.00 (t, J = 8.0 Hz, 1 H), 2.88-2.84 (t, J = 8.0 Hz, 2 H), 2.22 (s, 3 H), 1.57-1.50 (m, 2 H), 1.45-1.38 (m, 2 H), 1.23 (br s, 13 × 2 H), 0.86-0.82 (t, J = 8.0 Hz, 3 H) ppm. ¹³C NMR (100 MHz, DMSO-d 6): δ = 148.93, 139.97, 133.24, 124.36, 123.95, 122.73, 121.30, 119.64, 119.48, 117.48, 110.75, 101.87, 31.32, 29.36, 29.33, 29.14, 29.12, 29.05, 28.73, 28.12, 22.13, 13.97, 12.17 ppm. MS (EI): m/z (%) = 435 (100), 267 (10), 210 (38), 167 (4), 97 (3), 83 (4), 69 (5), 57 (7). HRMS (EI): m/z calcd for C30H45NO [M]+: 435.3501; found: 435.3500.

24

Spectral Data for Lipocarbazole A3 (1b)
IR (neat): ν = 3471, 3382, 2923, 2853, 1593, 1500, 1461, 1436, 1311, 1231, 1146, 1062, 831, 772, 739 cm-¹. ¹H NMR (400 MHz, DMSO-d 6): δ = 10.65 (s, 1 H), 8.79 (s, 1 H), 7.87-7.85 (d, J = 8.0 Hz, 1 H), 7.41-7.39 (d, J = 8.0 Hz, 1 H), 7.28-7.24 (t, J = 8.0 Hz, 1 H), 7.26 (s, 1 H), 7.04-7.00 (t, J = 8.0 Hz, 1 H), 5.35-5.27 (2 × 1 H), 2.89-2.85 (t, J = 8.0 Hz, 2 H), 2.22 (s, 3 H), 1.98-1.94 (m, 2 × 2 H), 1.57-1.50 (m, 2 H), 1.46-1.39 (m, 2 H), 1.29-1.21 (m, 9 × 2 H), 0.85-0.81 (t, J = 8.0 Hz, 3 H) ppm. ¹³C NMR (100 MHz, DMSO-d 6): δ = 149.00, 140.04, 133.31, 129.74, 129.71, 124.46, 124.02, 122.80, 121.37, 119.71, 119.57, 117.58, 110.83, 101.96, 31.36, 29.37, 29.22, 29.17, 29.01, 28.90, 28.77, 28.67, 28.19, 26.67, 26.65, 22.17, 14.02, 12.07 ppm. MS (EI): m/z (%) = 433 (94), 210 (100), 196 (6), 180 (12), 167 (11), 97 (3), 83 (4), 69 (5), 57 (8), 55 (9). HRMS (EI): m/z calcd for C30H43NO [M]+: 433.3345; found: 433.3342.

25

Spectral Data for Lipocarbazole A2 (1c)
IR (neat): ν = 3471, 3381, 3009, 2924, 2853, 1593, 1499, 1461, 1436, 1311, 1230, 1146, 1062, 831, 772, 739 cm-¹. ¹H NMR (400 MHz, DMSO-d 6): δ = 10.65 (s, 1 H), 8.79 (s, 1 H), 7.87-7.85 (d, J = 8.0 Hz, 1 H), 7.41-7.39 (d, J = 8.0 Hz, 1 H), 7.28-7.24 (t, J = 8.0 Hz, 1 H), 7.26 (s, 1 H), 7.04-7.00 (t, J = 8.0 Hz, 1 H), 5.37-5.25 (4 × 1H), 2.89-2.85 (t, J = 8.0 Hz, 2 H), 2.74-2.70 (t, J = 8.0 Hz, 2 H), 2.22 (s, 3 H), 2.00-1.97 (m, 2 × 2 H), 1.57-1.50 (m, 2 H), 1.46-1.39 (m, 2 H), 1.30-1.21 (m, 6 × 2 H), 0.85-0.81 (t, J = 8.0 Hz, 3 H). ¹³C NMR (100 MHz, DMSO-d 6): δ = 148.93, 139.96, 133.24, 129.72, 127.77, 127.73, 124.37, 123.94, 122.72, 121.30, 119.63, 119.49, 117.50, 110.75, 101.88, 30.89, 29.33, 29.30, 29.07, 28.95, 28.73, 28.10, 26.63, 26.61, 25.23, 21.97, 13.91, 11.99. MS (EI): m/z (%) = 431 (58), 210 (100), 196 (9), 180 (15), 167 (17), 91 (5). HRMS (EI): m/z calcd for C30H45NO [M]+: 431.3188; found: 431.3191.