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Synlett 2005(14): 2227-2229  
DOI: 10.1055/s-2005-872222
LETTER
© Georg Thieme Verlag Stuttgart · New York

Aiming for Branimycin: Synthesis of the cis-Decalin Core

Valentin S. Enev*, Martina Drescher, Hanspeter Kählig, Johann Mulzer*
Institute of Organic Chemistry, University of Vienna, Währingerstrasse 38, 1090 Vienna, Austria
Fax: +43(1)427752189; e-Mail: valentin.enev@univie.ac.at; e-Mail: johann.mulzer@univie.ac.at;
Further Information

Publication History

Received 9 May 2005
Publication Date:
20 July 2005 (online)

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Abstract

Starting from quinic acid, a highly substituted, cis-α,β unsaturated nitrile oxide was synthesiszed and involved in a 1,3-dipolar cycloaddition to afford a precursor of the cis-decalin system of branimycin.

Key words

branimycin - 1,3-dipolar cycloaddition - cis-α,β-unsaturated oximes - quinic acid

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4

Speitling, M.; Grün-Wollny, I.; Hannske, F. G.; Laatsch, H. 12 and 13 IRSEER Naturstofftage der DECHEMA e.V. Irsee 2000, 2001, poster sessions.

10

Selected Data.
Compound 18: IR (neat): 3344, 2947, 1613, 1514, 1463, 1376, 1249 cm-1. 1H NMR (600 MHz): δ = 7.62 (2 H, d, J = 7.7 Hz), 7.59 (2 H, d, J = 8Hz), 7.53 (1 H, dd, J = 10.5, 0.9 Hz) 7.46-7.32 (6 H, m), 7.27 (1 H, br s), 6.04 (1 H, ddd, J = 11.3, 9.1, 0.9 Hz), 5.79 (1 H, ddd, J = 11.4, 10.6, 1,2), 5.77 (2 H, m), 4.88 (1 H, ddd, J = 9.2, 2.1, 1.2 Hz), 4.41 (1 H, d, J = 7.0 Hz), 4.30 (1 H, d, J = 7Hz), 3.69 (1 H, ddd, J = 11.6, 8.7, 3.7 Hz), 3.36 (3 H, s), 3.31 (1 H, dd, J = 8.8, 6.4 Hz), 3.28 (1 H, dd, J = 8.9, 6.6 Hz), 3.24 (3 H, s), 2.50 (1 H, m), 2.21 (1 H, m), 2.15 (1 H, m), 1.32 (1 H, ddd, J = 12.3, 11.7, 11.7 Hz), 1.01 (9 H, s). 13C NMR (150 MHz): δ = 147.3 (CH), 139.8 (CH), 136.0 (CH), 135.9 (CH), 133.9 (C), 133.3 (C), 129.2 (CH), 129.7 (CH), 129.6 (CH), 127.6 (CH), 127.5 (CH), 125.6 (CH), 121.0 (CH), 96.4 (CH2), 76.8 (CH2), 75.8 (CH), 68.6 (CH), 58.9 (CH3), 55.4 (CH3), 51.3 (CH), 36.4 (CH), 32.8 (CH2), 26.9 (CH3), 19.5 (C). HRMS: m/z calcd for C30H41NO5Si: 523.2754; found: 523.2778.
Compound 19: IR (neat): 1922, 1560, 1456, 1377, 1197, 1122, 1072 cm-1. 1H NMR (600 MHz): δ = 7.75 (2 H, d, J = 6.8 Hz), 7.69 (2 H, d, J = 8.0 Hz), 7.50-7.30 (6 H, m), 6.30 (1 H, dd, J = 10.1, 2.8 Hz), 6.10 (1 H, ddd, J = 10.1, 1.5, 1.5 Hz), 4.83 (1 H, d, J = 6.9 Hz), 4.62 (1 H, d, J = 6.9 Hz), 4.60 (1 H, m), 4.41 (1 H, dd, J = 8.7, 8.7 Hz), 3.64 (1 H, ddd, J = 10.4, 10.4, 3.6 Hz), 3.47 (1 H, dd, J = 9.4, 4.7 Hz), 3.37 (1 H, dd, J = 9.4, 3.6 Hz), 3.10 (1 H, dd, J = 8.2, 5.8 Hz), 3.40 (3 H, s), 3.34 (3 H, s), 2.51 (1 H, m), 1.91 (1 H, ddd, J = 13.4, 3.7, 3.7 Hz), 1.66 (1 H, m), 1.35 (1 H, ddd, J = 13.4, 13.4, 10.9 Hz), 1.09 (9 H, s). 13C NMR (150 MHz): δ = 155.4 (C), 143.4 (CH), 136.0 (CH), 135,9 (CH), 133.1 (C), 127.8 (CH), 127.6 (CH), 129.9 (CH), 120.0 (CH), 117.0 (CH), 97.6 (CH2), 78.2 (CH), 73.5 (CH), 73.4 (CH2), 73.1 (CH), 59.2 (CH3), 55.7 (CH3), 48.6 (CH), 44.2 (CH), 38.1 (CH), 33.0 (CH2), 27.1 (CH3), 19.1 (C). HRMS: m/z calcd for C30H39NO5Si: 523.2598; found: 521.2584.

11

Selected NOE data for 19 is shown in Figure [1] .