Synthesis and Absolute Configuration of the Supposed Structure of Cladocoran A and B

I. S. Marcos; A. B. Pedrero; M. J. Sexmero; D. Diez; P. Basabe; F. A. Hernández; H. B. Broughton; J. G. Urones

doi:10.1055/s-2002-19318

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Synlett 2002(1): 0105-0109
DOI: 10.1055/s-2002-19318

LETTER

Synthesis and Absolute Configuration of the Supposed Structure of Cladocoran A and B

I. S. Marcos*^a, A. B. Pedrero^a, M. J. Sexmero^a, D. Diez^a, P. Basabe^a, F. A. Hernández^a, H. B. Broughton^b, J. G. Urones^a
^a Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad de Salamanca, Plaza de los Caídos 1-5, 37008 Salamanca, Spain
Fax: +34(923)294574; e-Mail: ismarcos@usal.es;
^b Merck Sharp and Dohme, Harlow, Essex, UK

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Publication History

Received 25 June 2001
Publication Date:
01 February 2007 (online)

Abstract
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Abstract

The proposed structures of cladocoran A and B, sesterterpenoid γ-hydroxybutenolides, were synthesized from ent-halimic acid.

Key words

cladocoran A and B - ent-halimic acid - dysidiolide - diterpenes - sesterterpenes

References

1 Fontana A. Ciavatta ML. Cimino G. J. Org. Chem. 1998, 63: 2845

Crossref Google Scholar
2 Gunasekera GP. Mc Carthy PJ. Kelly-Borges M. Lobkovsky E. Clardy J. J. Am. Chem. Soc. 1996, 118: 8759

Crossref Google Scholar
3 Corey EJ. Roberts BE. J. Am. Chem. Soc. 1997, 119: 12425

Crossref Google Scholar
4 Magnuson SR. Sepp-Lorenzino L. Rosen N. Danishefsky SJ. J. Am. Chem. Soc. 1998, 120: 1615

Crossref Google Scholar
5 Boukouvalas J. Cheng Y.-X. Robichaud J. J. Org. Chem. 1998, 63: 288

Google Scholar
6a Miyaoka H. Kajiwara Y. Yamada Y. Tetrahedron Lett. 2000, 41: 911

Crossref Google Scholar
6b Miyaoka H. Kajiwara Y. Hara Y. Yamada Y. J. Org. Chem. 2001, 66: 1429

Crossref Google Scholar
7 Jung ME. Nishimura N. Org. Lett. 2001, 3: 2113

Crossref Google Scholar
8a Takahashi M. Dodo K. Hashimoto Y. Shirai R. Tetrahedron Lett. 2000, 41: 2111

Crossref Google Scholar
8b Takahashi M. Dodo K. Sugimoto Y. Aoyagui Y. Yamad Y. Hashimoto Y. Shirai R. Bioorg. Med. Chem. Lett. 2000, 10: 2571

Crossref Google Scholar
8c Blanchard JL. Epstein DM. Boisclair MD. Rudolph J. Pal K. Bioorg. Med. Chem. Lett. 1999, 9: 2537

Crossref Google Scholar
9 Brohm D. Waldmann H. Tetrahedron Lett. 1998, 39: 3995

Crossref Google Scholar
10a Piers E. Caillé S. Chen G. Org. Lett. 2000, 2: 2483

Crossref Google Scholar
10b Paczkowski R. Maichle-Mössmer C. Maier ME. Org. Lett. 2000, 2: 3967

Crossref Google Scholar
11 Demeke D. Forsyth CJ. Org. Lett. 2000, 2: 3177

Crossref Google Scholar
12 Conte MR. Fattorusso E. Lanzotti V. Magno S. Mayol L. Tetrahedron 1994, 50: 849

Crossref Google Scholar
13 Lombardo D. Dennis EA. J. Biol. Chem. 1985, 260: 7234

Google Scholar
14 Sullivan B. Faulkner DJ. Tetrahedron Lett. 1982, 23: 907

Crossref Google Scholar
15 De Rosa S. De Stefano S. Zavodnik N. J. Org. Chem. 1988, 53: 5020

Google Scholar
16 Urones JG. Pascual Teresa J. Marcos IS. Díez D. Garrido NM. Guerra RA. Phytochemistry 1987, 26: 1077

Crossref Google Scholar
17a Marcos IS. González JL. Sexmero MJ. Díez D. Basabe P. Williams DJ. Simmonds MSJ. Urones JG. Tetrahedron Lett. 2000, 41: 2553

Google Scholar
17b Marcos IS. Sexmero MJ. Pedrero AB. Hernández FA. González E. Urones JG. Chimia 1999, 53: 368

Google Scholar
18 Kernan MR. Faulkner DJ. J. Org. Chem. 1988, 53: 2773

Crossref Google Scholar
19 Urones JG. Marcos IS. Basabe P. Garrido NM. Jorge A. Moro RF. Lithgow AM. Tetrahedron 1993, 49: 6079

Crossref Google Scholar
20 Ley SV. Norman J. Griffith WP. Marsden SP. Synthesis 1994, 639

Article in Thieme Connect Google Scholar
21a Liu HJ. Shia K.-S. Tetrahedron 1998, 54: 13449

Google Scholar
21b Levine SJ. J. Am. Chem. Soc. 1958, 80: 6150

Google Scholar
21c Wittig G. Schlosser M. Chem. Ber. 1961, 94: 1383

Google Scholar
21d Wittig G. Böll W. Krück K.-H. Chem. Ber. 1962, 95: 2514

Google Scholar
21e Wittig G. Angew. Chem. 1956, 68: 505

Google Scholar
22 Marcos IS. Moro RF. Carballares S. Urones JG. Synlett 2000, 4: 541

Article in Thieme Connect Google Scholar
23 Giner JL. Margot C. Djerassi C. J. Org. Chem. 1989, 54: 369

Google Scholar
24 Marcos IS. Moro RF. Carballares S. Urones JG. Tetrahedron 2001, 57: 713

Crossref Google Scholar

25

Crystal data for 11: C₂₁H₃₂O₃, M = 332.47, orthorhombic, space group P2₁2₁2₁ (nº 19). a = 7.6504(15), b = 8.771(2), c = 28.694(6) Å, V = 1925.4(7) Å³, Z = 4, D_c = 1.147 mg/m³, m (Cu-K_α) = 0.075 mm^-1, F(000) = 728. Data (3609 collected reflections, and 3331 unique reflections [I > 2sigma (I)]) were measured on a Seifert 3003 SC rotating anode diffractometer with Cu-K_α radiation (graphite monochromator) using 2θ-ω scans at 268 K. The structure was solved by direct methods and the non-hydrogen atoms were refined anisotropically by full-matrix least squares based on F² to give the agreement factors R₁ =& nbsp;0.0669, wR₂ = 0.1527. Computations were carried on a Digital Alphastation 500 using the SHELXTL^Τ ^Μ program. Crystallographic data for the structure of 11 in this paper have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 163376. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, (UK), (fax: +44(1223)336033 or e-mail: deposit@ccdc.cam.ac.uk).

26

The assignments for the spectra, ¹H NMR and ¹³C NMR for 1 and 2 were done by bidimensional experiments HMQC and HMBC. Spectroscopic and physical data for the mixture of α- and β-epimers at C₂₀ in 1: R_f = 0.41 (hexane-EtOAc, 7:3, v/v); [α]_D: +20.0 (c 0.47, CHCl₃); UV/Vis (EtOH): λ_max = 207 nm (ε 8500); IR(film): ν_max 3422, 3071, 3051, 2938, 2870, 1794, 1771, 1719, 1653, 1458, 1373, 1250, 1123, 1038, 939, 885 cm^-1; MS (EI): m/z (%) = 444(1) [M⁺], 384(8), 340(13), 301(25), 259(44), 173(58), 105(62), 81(57); HRMS: m/z calcd for C₂₇H₄₀O₅: 444.2876; found: 444.2911. Data for major epimer: ¹H NMR (CDCl₃, 400 MHz): δ = 5.99 (1 H, d, J = 9.4 Hz, H-20), 5.92 (1 H, s, H-21), 5.46 (1 H, m, H-10), 5.29 (1 H, dd, J = 3.0, 7.0 Hz, H-18), 4.94 (1 H, d, J = 9.4 Hz, OH), 4.70 (1 H, s, H_A-3), 4.66 (1 H, s, H_B-3), 2.56 (1 H, dd, J = 7.0, 15.2 Hz, H_A-17), 2.01 (3 H, s, -OOCMe), 1.97 (2 H, t, J = 7.2 Hz, H-4), 1.88 (2 H, m, H-13), 1.87 (1 H, m, H-12), 1.82 and 1.37 (1 H, m ea, H-14), 1.71 (3 H, s, Me-1), 1.60 (1 H, dd, J = 3.0, 15.2 Hz, H_B-17), 1.57 (2 H, m, H-9), 1.56 (1 H, m, H-15), 1.41 and 1.19 (1 H, m ea, H-8), 1.35 and 1.23 (1 H, m ea, H-5), 1.28 and 1.21 (1 H, m ea, H-6), 0.97 (3 H, s, Me-25), 0.84 (3 H, d, J = 7.2 Hz, Me-24), 0.80 (3 H, s, Me-23); ¹³C NMR (CDCl₃, 100 MHz): δ = 22.4 (C-1), 146.0 (C-2), 109.7 (C-3), 38.5 (C-4), 21.5 (C-5), 40.2 (C-6), 34.2 (C-7), 31.7 (C-8), 21.7 (C-9), 121.8 (C-10), 140.1 (C-11), 41.7 (C-12), 22.7 (C-13), 28.4 (C-14), 38.6 (C-15), 42.4 (C-16), 43.1 (C-17), 67.7 (C-18), 168.8 (C-19), 97.7 (C-20), 117.9 (C-21), 169.5 (C-22), 21.5 (C-23), 15.5 (C-24), 23.8 (C-25), 171.2 (-OOCMe), 21.0 (-OOCMe). Data for minor epimer: ¹H NMR (CDCl₃, 400 MHz): δ = 6.20 (1 H, br s, H-20), 5.96 (1 H, s, H-21), 5.46 (1 H, m, H-10), 5.44 (1 H, dd, J = 3.0, 8.0 Hz, H-18), 4.70 (1 H, s, H_A-3), 4.66 (1 H, s, H_B-3), 4.38 (1 H, br s, OH), 2.38 (1 H, dd, J = 8.0, 15.2 Hz, H_A-17), 2.03 (3 H, s, -OOCMe), 1.97 (2 H, t, J = 7.2 Hz, H-4), 1.92 (1 H, m, H-12), 1.88 (2 H, m, H-13), 1.88 and 1.42 (1 H, m ea, H-14), 1.83 (1 H, dd, J = 3.0, 15.2 Hz, H_B-17), 1.71 (3 H, s, Me-1), 1.57 (2 H, m, H-9), 1.56 (1 H, m, H-15), 1.33 and 1.09 (1 H, m ea, H-8), 1.35 and 1.23 (1 H, m ea, H-5), 1.28 and 1.21 (1 H, m ea, H-6), 0.97 (3 H, s, Me-25), 0.84 (3 H, d, J = 7.2 Hz, Me-24), 0.80 (3 H, s, Me-23); ¹³C NMR (CDCl₃, 100 MHz): δ = 22.4 (C-1), 146.0 (C-2), 109.7 (C-3), 38.5 (C-4), 21.5 (C-5), 40.2 (C-6), 34.2 (C-7), 31.9 (C-8), 21.7 (C-9), 121.1 (C-10), 140.1 (C-11), 41.4 (C-12), 22.7 (C-13), 28.2 (C-14), 38.6 (C-15), 42.4 (C-16), 42.4 (C-17), 67.3 (C-18), 167.8 (C-19), 97.9 (C-20), 118.8 (C-21), 169.5 (C-22), 21.5 (C-23), 15.5 (C-24), 23.5 (C-25), 171.2 (-OOCMe), 21.0 (-OOCMe). Spectroscopic and physical data for the mixture of α- and β-epimers at C₂₀ in 2: R_f = 0.45 (hexane-EtOAc, 6:4, v/v); [α]_D: +98.9 (c 0.64, CHCl₃); UV/Vis (EtOH): λ_max = 205 nm (ε 8600); IR(film): ν_max 3378, 3074, 3052, 2938, 1753, 1649, 1451, 1377, 1263, 1136, 953, 885, 739 cm^-1; MS (FAB) m/z (%) = 403(6) [M⁺ +1], 385(12), 367(16), 259(34), 154(100), 91(58); HRMS (FAB) m/z calcd for [C₂₅H₃₈O₄ + H]⁺: 403.2848; found: 403.2823. Data for major: ¹H NMR (CDCl₃, 400 MHz): δ = 6.06 (1 H, d, J = 6.8 Hz, H-20), 6.02 (1 H, br s, H-21), 5.66 (1 H, m, H-10), 4.80 (1 H, dd, J = 10.0, 1.8 Hz, H-18), 4.71 (1 H, s, H_A-3), 4.67 (1 H, s, H_B-3), 4.50 (1 H, d, J = 6.8 Hz, OH), 2.81 (1 H, d, J = 1.8 Hz, OH), 2.56 (1 H, dd, J = 10.0, 14.0 Hz, H_A-17), 2.16 (1 H, m, H-12), 2.06 (2 H, m, H-9), 1.97 (2 H, m, H-4), 1.71 (3 H, s, Me-1), 1.59 (2 H, m, H-13), 1.58 (1 H, m, H-15), 1.42 (2 H, m, H-5), 1.39 and 1.16 (1 H, m ea, H-8), 1.35 (2 H, m, H-14), 1.34 (1 H, d, J = 14.0 Hz, H_B-17), 1.23 and 1.18 (1 H, m ea, H-6), 1.11 (3 H, s, Me-25), 0.83 (3 H, d, J = 7.0 Hz, Me-24), 0.82 (3 H, s, Me-23); ¹³C (CDCl₃, 100 MHz): = δ 22.3 (C-1), 146.4 (C-2), 109.6 (C-3), 38.5 (C-4), 21.3 (C-5), 39.4 (C-6), 34.1 (C-7), 31.3 (C-8), 22.8 (C-9), 122.7 (C-10), 143.6 (C-11), 41.1 (C-12), 22.7 (C-13), 28.3 (C-14), 40.5 (C-15), 42.7 (C-16), 44.9 (C-17), 66.8 (C-18), 171.1 (C-19), 97.3 (C-20), 117.1 (C-21), 170.6 (C-22), 21.3 (C-23), 15.4 (C-24), 22.1 (C-25). Data for minor: ¹H NMR (CDCl₃, 400 MHz): δ = 6.20 (1 H, d, J = 6.8 Hz, H-20), 5.96 (1 H, br s, H-21), 5.66 (1 H, m, H-10), 4.76 (1 H, dd, J = 10.0, 1.8 Hz, H-18), 4.69 (1 H, s, H_A-3), 4.65 (1 H, s, H_B-3), 4.50 (1 H, d, J = 6.8 Hz, OH), 2.86 (1 H, d, J = 1.8 Hz, OH), 2.56 (1 H, dd, J = 10.0, 14.0 Hz, H_A-17), 2.11 (1 H, m, H-12), 2.06 (2 H, m, H-9), 1.97 (2 H, m, H-4), 1.69 (3 H, s, Me-1), 1.59 (2 H, m, H-13), 1.58 (1 H, m, H-15),1.57 (1 H, d, J = 14.0 Hz, H_B-17), 1.42 (2 H, m, H-5), 1.46 and 1.23 (1 H, m ea, H-8), 1.40 (2 H, m, H-14), 1.23 and 1.18 (1 H, m ea, H-6), 1.09 (3 H, s, Me-25), 0.83 (3 H, d, J = 7.0 Hz, Me-24), 0.82 (3 H, s, Me-23); ¹³C NMR (CDCl₃, 100 MHz): δ = 22.3 (C-1), 146.1 (C-2), 109.7 (C-3), 38.5 (C-4), 21.3 (C-5), 39.5 (C-6), 34.1 (C-7), 31.3 (C-8), 22.8 (C-9), 122.6 (C-10), 143.8 (C-11), 41.4 (C-12), 22.7 (C-13), 28.3 (C-14), 40.4 (C-15), 42.5 (C-16), 44.2 (C-17), 66.3 (C-18), 169.8 (C-19), 97.8 (C-20), 117.5 (C-21), 170.7 (C-22), 21.4 (C-23), 15.4 (C-24), 22.2 (C-25).