Artículos de revistas
Coibacins A And B: Total Synthesis And Stereochemical Revision
Registro en:
Journal Of Organic Chemistry. American Chemical Society, v. 79, n. 2, p. 630 - 642, 2014.
223263
10.1021/jo402339y
2-s2.0-84896768719
Autor
Carneiro V.M.T.
Avila C.M.
Balunas M.J.
Gerwick W.H.
Pilli R.A.
Institución
Resumen
The interface between synthetic organic chemistry and natural products was explored in order to unravel the structure of coibacin A, a metabolite isolated from the marine cyanobacterium cf. Oscillatoria sp. that exhibits selective antileishmanial activity and potent antiinflammatory properties. Our synthetic plan focused on a convergent strategy that allows rapid access to the desired target by coupling of three key fragments involving E-selective Wittig and modified Julia olefinations. CD measurements and comparative HPLC analyses of the natural product and four synthetic stereoisomers led to determination of its absolute configuration, thus correcting the original assignment at C-5 and unambiguously establishing those at C-16 and C-18. Additionally, we synthesized coibacin B on the basis of the assignment of configuration for coibacin A. © 2013 American Chemical Society. 79 2 630 642 Gerwick, W.H., Moore, B.S., (2012) Chem. Biol., 19, p. 85 Lewy, D., Gauss, C.-M., Soenen, D., Boger, D., (2002) Curr. Med. Chem., 9, p. 2005 Stampwala, S.S., Bunge, R.H., Hurley, T.R., Willmer, N.E., Brankiewicz, A.J., Steinman, C.E., Smitka, T.A., French, J.C., (1983) J. Antibiot., 36, p. 1601 Tunac, J.B., Graham, B.D., Dobson, W.E., (1983) J. Antibiot., 36, p. 1595 Kalesse, M., Christmann, M., (2002) Synthesis, 981 Kobayashi, M., Higuchi, K., Murakami, N., Tajima, H., Aoki, S., (1997) Tetrahedron Lett., 38, p. 2859 Murakami, N., Wang, W., Aoki, M., Tsutsui, Y., Higuchi, K., Aoki, S., Kobayashi, M., (1997) Tetrahedron Lett., 38, p. 5533 Maier, M.E., (2009) Nat. Prod. Rep., 26, p. 1105 Nicolaou, K.C., Snyder, S.A., (2005) Angew. Chem. Int. Ed., 44, p. 1012 Balunas, M.J., Grosso, M.F., Villa, F.A., Engene, N., McPhail, K.L., Tidgewell, K., Pineda, L.M., Gerwick, W.H., (2012) Org. Lett., 14, p. 3878 Gerwick, W.H., Proteau, P.J., Nagle, D.G., Hamel, E., Blokhin, A., Slate, D.L., (1994) J. Org. Chem., 59, p. 1243 Edwards, D.J., Marquez, B.L., Nogle, L.M., McPhail, K., Goeger, D.E., Roberts, M.A., Gerwick, W.H., (2004) Chem. Biol., 11, p. 817 Green, L.C., Wagner, D.A., Glogowski, J., Skipper, P.L., Wishnok, J.S., Tannenbaum, S.R., (1982) Anal. Biochem., 126, p. 131 Barcelos, R., Pastre, J., Caixeta, V., Vendramini-Costa, D., De Carvalho, J., Pilli, R., (2012) Bioorg. Med. Chem., 20, p. 3635 Bruder, M., Vendramini-Costa, D., De Carvalho, J., Pilli, R., (2013) Bioorg. Med. Chem., 21, p. 5107 De Fatima, A., Kohn, L.K., Antonio, M., De Carvalho, J., Pilli, R., (2005) Bioorg. Med. Chem., (13), p. 2927 De Fatima, A., Kohn, L.K., De Carvalho, J., Pilli, R., (2006) Bioorg. Med. Chem., (14), p. 622 Vendramini-Costa, D., De Castro, B.I.D., Ruiz, A., Marquissolo, C., Pilli, R., De Carvalho, J., (2010) Bioorg. Med. Chem., 18, p. 6742 Boger, D.L., Ichikawa, S., Zhong, W., (2001) J. Am. Chem. Soc., 123, p. 4161 Crimmins, M.T., King, B.W., (1998) J. Am. Chem. Soc., 120, p. 9084 Phillips, D.J., Pillinger, K.S., Li, W., Taylor, A.E., Graham, A.E., (2006) Chem. Commun., 2280 Charette, A.B., Juteau, H., (1994) J. Am. Chem. Soc., 116, p. 2651 Although an axial orientation of the isopropyl substituent can be assumed on the basis of the anomeric effect, we have refrained from depicting the stereochemistry at C-1 because of a lack of unambiguous evidence, as the NOESY spectrum does show a weak correlation between H-1 and H5Correa Jr., I., Pilli, R., (2003) Angew. Chem., Int. Ed., (42), p. 3017 Charette, A.B., Lebel, H., (1996) J. Am. Chem. Soc., 118, p. 10327 Chiralpak IA column (particle size 5 μm, dimensions 4.6 mm × 250 mm, 98% hexanes/2% i-PrOH, 1 mL/min). For chromatograms, see the Supporting InformationTamura, R., Saegusa, K., Kakihana, M., Oda, D., (1988) J. Org. Chem., 53, p. 2723 Aissa, C., (2009) Eur. J. Org. Chem., 1831 Liu, P., Jacobsen, E.N., (2001) J. Am. Chem. Soc., 123, p. 10772 Smith III, A.B., Brandt, B., (2001) Org. Lett., 3, p. 1685 The yield and diastereoisomeric ratio for the preparation of (5S,16S,18S)-25 were not optimized because they were obtained before the studies shown in Table 1Li, D., Zhao, Y., Ye, L., Chen, C., Zhang, J., (2010) Synthesis, p. 3325 SunFire Prep C18 OBD column (particle size 5 μm, dimensions 19 mm × 100 mm, 60% MeCN/40% H2O, 17 mL/min)Chiralpak IA (particle Size 5 μm Dimensions 4.6 Mm × 250 Mm 90% MeCN10% MeOH 0.7 MLmin). For chromatograms, see the Supporting InformationBeecham, A., (1972) Tetrahedron, 28, p. 5543 Nagle, D.G., Geralds, R.S., Yoo, H.-D., Gerwick, W.H., Kim, T.-S., Nambu, M., White, J., (1995) Tetrahedron Lett., 36, p. 1189 Gu, L., Wang, B., Kulkarni, A., Geders, T.W., Grindberg, R.V., Gerwick, L., Hakansson, K., Sherman, D., (2009) Nature, 459, p. 731 SunFire Prep C18 OBD column (particle size 5 μm, dimensions 19 mm × 100 mm, 55% MeCN/45% H2O, 17 mL/min)Guivisdalsky, P.N., Bittman, R., (1989) J. Org. Chem., 54, p. 4637 Huckins, J.R., De Vicente, J., Rychnovsky, S.D., (2007) Org. Lett., 9, p. 4757 Stempel, G.H., Cross, R.P., Mariella, R.P., (1950) J. Am. Chem. Soc., 72, p. 2299 Kamal, A., Balakrishna, M., Reddy, P.V., Faazil, S., (2010) Tetrahedron: Asymmetry, 21, p. 2517 Hansen, T., (2002) Tetrahedron: Asymmetry, 13, p. 547 Fox, R.J., Lalic, G., Bergman, R.G., (2007) J. Am. Chem. Soc., 129, p. 14144 Kelly, B.D., Lambert, T.H., (2011) Org. Lett., 13, p. 740 Bahde, R.J., Rychnovsky, S.D., (2008) Org. Lett., 10, p. 4017