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    B. Schlegel, A. Hartl, H. M. Dahse, F. A. Gollmick, U. Gräfe, H. Dorfelt, B. Kappes, J. Antibiot. 2002, 55, 814.
  • 2
    J. J. La Clair, unpublished results.
  • 3
    Bis(acetate) 4 was prepared according to the procedure reported in: M. Tanaka, Y. Norimine, T. Fujita, H. Suemune, K. Sakai, J. Org. Chem. 1996, 61, 6952.
  • 4
    G. Stork, M. Kahn, J. Am. Chem. Soc. 1985, 107, 500.
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    A. B. Smith III, D. Lee, C. M. Adams, M. C. Kozlowski, Org. Lett. 2002, 4, 4539.
  • 6
    SmI2 as suggested by Smith et al.[5] also failed. An alternative synthesis using a triethylsilylcyanohydrin was used to alleviate concerns over the use of a dithiane. Details of this route shall be explained in forthcoming publications.
  • 7
    Epoxide 15 was prepared using a method described in: G. Anker, J. Attaghrai, D. Picq, D. Anker, Carbohydr. Res. 1987, 159, 159.
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    T. Cohen, J. R. Matz, J. Am. Chem. Soc. 1980, 102, 6900.
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    The primary mesylate of 24 c was the major product obtained by treating 23 a,b with MsCl in pyridine. The reversibility of mesylation with sulfene was previously described for cyclization procedures: P. T. Lansbury, J. J. La Clair, Tetrahedron Lett. 1993, 34, 4431.chemical structure image
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    C. Li, R. P. Johnson, J. A. Porco, Jr., J. Am. Chem. Soc. 2003, 125, 5095.
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    D. R. Williams, D. C. Kammler, A. F. Donnell, W. R. F. Goundry, Angew. Chem. 2005, 117, 6873; Angew. Chem. Int. Ed. Angew. Chem. Int. Ed. Engl. 2005, 44, 6715.
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    D. M. Nowak, P. T. Lansbury, Tetrahedron 1998, 54, 319.
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  • 16a
    T. Tamai, K. Mizuno, I. Iiashida, Y. Otsuji, Tetrahedron Lett. 1993, 34, 2641;
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    V.-H. Nguyen, H. Nishino, K. Kazu, Tetrahedron Lett. 1997, 38, 1773.
  • 17
    Physical and spectral properties of 1: Colorless solid; m.p.: 172–174 °C; Rf=0.83 in CH3Cl/MeOH (9:1 v/v); IR (film): equation image=3417, 3018, 2985, 2935, 1699, 1625, 1382, 1214, 1009, 1132, 996, 982, 910 cm−1; 1H NMR (500 MHz, CDCl3+1 % CD3OD, J [Hz]): δ=6.73 (dd, J=5.3, 2.4, 1 H), 5.46 (d, J=10.1, 1 H), 4.99 (br dd, J=5.2, 1 H), 4.81 (d, J=10.1, 1 H), 3.81 (dd, J=9.5, 1.6, 1 H), 3.64 (m, 1 H), 3.59 (d, J=5.3,1 H), 3.55 (m, 1 H), 3.51 (dd, J=2.8, 0.5, 1 H), 3.29 (d, J=3.0, 1 H), 3.24 (d, J=3.6, 1 H), 3.03 (s, 3 H), 2.75 (dd, J=5.2, 7.9, 1 H), 1.77 (s, 3 H), 1.73 (s, 3 H), 1.27 (s, 3 H), 1.15 ppm (s, 3 H); HR-EIMS: calcd m/z: 416.1835; found: 416.1892. See Supporting Information for spectra.
  • 18
    Physical and spectral properties of 2: Colorless solid; m.p.: 165–169 °C; Rf=0.79 in CH3Cl/MeOH (9:1 v/v); IR (film): equation image=3418, 3015, 2980, 2932, 1701, 1626, 1380, 1216, 1005, 1131, 995, 981, 912 cm−1; 1H NMR (500 MHz, CDCl3+1 % CD3OD, J [Hz]): δ=6.78 (dd, J=5.4, 2.2, 1 H), 5.41 (d, J=10.6, 1 H), 5.01 (br dd, J=5.2, 1 H), 4.56 (d, J=8.2, 1 H), 3.76 (dd, J=9.5, 1.6, 1 H), 3.58 (m,1 H), 3.52 (m, 1 H), 3.51 (d, J=5.2, 1 H), 3.48 (dd, J=2.9, 0.5, 1 H), 3.32 (d, J=2.8, 1 H), 3.26 (d, J=3.4, 1 H), 3.08 (s, 3 H), 2.78 (dd, J=5.1, 7.8, 1 H), 1.81 (s, 3 H), 1.72 (s, 3 H), 1.28 (s, 3 H), 1.17 ppm (s, 3 H); HR-EIMS: calcd m/z: 416.1835; found: 416.1881. See Supporting Information for spectra.
  • 19
    Physical and spectral properties of 3 as a 1:1 mixture of olefin isomers: Waxy solid; Rf=0.68 in CH3Cl/MeOH (12:1 v/v); IR (film): equation image=3417, 2965, 2955, 1695, 1624, 1422, 1272, 1104, 1002, 992, 972, 912 cm−1; 1H NMR (500 MHz, CDCl3+1 % CD3OD, J [Hz]): δ=6.90 (d, J=9.2, 1.3, 1 H); 6.94 (d, J=10.5, 0.7, 1 H), 5.92 (d, J=9.3, 1.2, 1 H); 5.89 (d, J=10.5, 0.7, 1 H), 5.79 (dd, J=5.3, 2.4, 1 H), 5.56 (dd, J=9.3, 2.4, 1 H), 5.22 (dd, J=9.3,1.8, 1 H), 3.65 (dd, J=2.1, 0.8, 1 H), 3.51 (dd, J=2.3, 1.8, 1 H), 3.31 (m, 1 H), 3.21 (dd, J=8.4, 1.1, 1 H), 3.16 (br d, J=2.6, 1 H), 3.16 (d, J=2.0, 1 H), 3.06 (m, 1 H) , 2.82 (s, 3 H), 1.76 (s, 3 H), 1.75 (s, 3 H), 1.21 (s, 3 H), 1.18 ppm (s, 3 H); HR-EIMS: calcd m/z: 384.1937; found: 384.1911. See Supporting Information for spectra.
  • 20
    W. Peters, B. L. Robinson, Ann. Trop. Med. Parasitol. 1999, 93, 325.
  • 21
    A. M. Szpilman, E. E. Korshin, H. Rozenberg, M. D. Bachi, J. Org. Chem. 2005, 70, 3618.
  • 22
    Note added in proof: The 1H NMR spectra for this Communication were determined by contract services. The spectra provided in the Supporting Information were collected by N. Voss (Berlin, Germany). The operator added the peak for CDCl3 to the spectrum of synthetic hexacyclinol (1), however, this was done incorrectly at δ≈7.5 ppm and against the request of the author. Additionally, one spectrum was duplicated and a copy of the spectra for natural 5-epi-hexacyclinol was not provided.