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Volumn 14, Issue 9, 2008, Pages 2867-2885

Synthesis of (+)-obtusenyne

Author keywords

Claisen rearrangement; Hydrosilation; Medium rings; Natural products; Total synthesis

Indexed keywords

HALOGENATION; HYDROSILYLATION; ORGANIC COMPOUNDS; OXYGEN; RAW MATERIALS; SUGAR (SUCROSE);

EID: 53849140858     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200701567     Document Type: Article
Times cited : (27)

References (98)
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    • For a recent review see reference [1c].
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    • For our previous work on the synthesis of obtusenyne see: a
    • For our previous work on the synthesis of obtusenyne see: a) N. R. Curtis, A.B. Holmes, M.G. Looney, Tetrahedron 1991, 47, 7171;
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    • Molecular modelling was conducted with in vacuo simulation by using a Monte Carlo conformational search (G. Chang, W. C. Guida, W. C. Still. J. Am. Chem. Soc. 1989, 111, 4379) by using the MM2* forcefield (N. L. Allinger, J. Am. Chem. Soc. 1977, 99, 8127) as implemented in MacroModel v 8.0. MacroModel is available from Schrödinger (http://www.schrodinger.com).
    • Molecular modelling was conducted with in vacuo simulation by using a Monte Carlo conformational search (G. Chang, W. C. Guida, W. C. Still. J. Am. Chem. Soc. 1989, 111, 4379) by using the MM2* forcefield (N. L. Allinger, J. Am. Chem. Soc. 1977, 99, 8127) as implemented in MacroModel v 8.0. MacroModel is available from Schrödinger (http://www.schrodinger.com).
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    • 2-enol ether in a tetrahydrooxonine see: K. C. Nicolaou, C. V. C. Prasad, W. W. Ogilvie, J. Am. Chem. Soc. 1990, 112, 4988.
    • 2-enol ether in a tetrahydrooxonine see: K. C. Nicolaou, C. V. C. Prasad, W. W. Ogilvie, J. Am. Chem. Soc. 1990, 112, 4988.
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    • We encountered similar problems when attempting analogous hydroborations in the eight-membered ring series: see reference [6,15,16
    • We encountered similar problems when attempting analogous hydroborations in the eight-membered ring series: see reference [6,15,16].
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    • 84921424906 scopus 로고    scopus 로고
    • X-ray crystallography structure determination of the bicyclic ether (±)-23: Crystal data: Empiracal formula: C33H 42O3SeSi; Mw, 593; colourless block, 0.38×0.22×0.14 mm3: orthorhombic P212 121 (no.19, a, 12.032(2, b= 14.869(2, c= 17.197(4) Å; V=3074(1) Å3: Z, 4; T=298(2)°K; DX, 1.28 g cm-3; λ, 1.5418 Å; μ, 1.688 mm-1; Nicolet R3 diffractometer: 3.74°<θ<60°: 4988 measured reflections. 4428 independent. The structure was solved by direct methods (SHELX. reference [31, and refined by least squares (SHELX, reference [31, to R1 =0.053. wR2, 0.058 (all data, The original data and computer files for this structure are lost; this information and the coordinate data were retrieved from the printed pages of a thesis. b) CCDC 65
    • 2 = 0.058 (all data). The original data and computer files for this structure are lost; this information and the coordinate data were retrieved from the printed pages of a thesis. b) CCDC 655152 ((±)-23), 655151 ((-)-54), 655143 ((-)-57) and 655147 ((-)-38) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif
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    • G. M. Sheldrick, SHELXS-97/SHELXL-97. University of Göttingen, 1997 (Germany).
    • G. M. Sheldrick, SHELXS-97/SHELXL-97. University of Göttingen, 1997 (Germany).
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    • 3 to convert a medium-ring alcohol into the corresponding bromide see: references [6.11,13] and K. Fujiwara, S. Yoshimoto, A. Takizawa, S. Souma, H. Mishima, A. Murai, H. Kawai, T. Suzuki, Tetrahedron Lett. 2005, 46, 6819;
    • 3 to convert a medium-ring alcohol into the corresponding bromide see: references [6.11,13] and K. Fujiwara, S. Yoshimoto, A. Takizawa, S. Souma, H. Mishima, A. Murai, H. Kawai, T. Suzuki, Tetrahedron Lett. 2005, 46, 6819;
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    • Reduction of the corresponding benzylidene acetal took 96 h at room temperature see reference [8b
    • Reduction of the corresponding benzylidene acetal took 96 h at room temperature see reference [8b].
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    • For reviews see:, Eds, J.P. Tierney, P. Lidström, Blackwell, Oxford
    • For reviews see: Microwave Assisted Organic Synthesis (Eds.: J.P. Tierney, P. Lidström), Blackwell, Oxford. 2005;
    • (2005) Microwave Assisted Organic Synthesis
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    • For a recent example of the use of microwaves to accelerate a Claisen rearrangement for the construction of a medium ring see: X. Li, R. E. Kyne, T. V. Ovaska, Tetrahedron 2007, 63, 1899
    • For a recent example of the use of microwaves to accelerate a Claisen rearrangement for the construction of a medium ring see: X. Li, R. E. Kyne, T. V. Ovaska, Tetrahedron 2007, 63, 1899.
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    • 84921424901 scopus 로고    scopus 로고
    • X-ray crystallographic structure determination of, )-54: Crystal data: Empirical formula: C30H43ClO4Si; M w, 531.18; colourless block, 0.23×0.09×0.09 mm 3; monoclinic P21 (no. 4, a, 13.0614(8, b, 8.1844(3, c= 14.0059(8) Å β= 95.253(2)°: V= 1490.9(2) Å3; Z, 2; T=180(2)°K, DX=1.183 g cm-3; λ=0.71073 Å;; μ, 0.200 mm -1, Nonius Kappa CCD diffractometer equipped with an Oxford Cryosystems Cryostream cooling apparatus: 3.58°<θ<25. 04°: 8936 measured reflections: 4937 independent (Rint, 0.034, 4288 with I> 4σ(I, The structure was solved by direct methods (SHELXS-97, reference [31, and refined by least squares SHELXL-97, reference [31, by using Chebyshev weights on Fo2 to R
    • -3.
  • 82
    • 84921424900 scopus 로고    scopus 로고
    • X-ray crystallographic structure determination of, )-57: Crystal data: Empirical formula, C18H2:3ClO5·1/ 2(H2O, Mw=727.64; colourless block. 0.46×0.05×0.05mm3; monoclinic P2̄1 (no. 4, a, 14.2670(3, b= 4.6914(1, c, 26.6612(9) Å; β= 99.77953(1)°: V, 1758.56(8) Å3; Z, 4, T=240(2)°K: DX, 1.374 g cm-3; λ, 0.71073 Å; μ =0.245 mm-1: Nonius Kappa CCD diffractometer equipped with an Oxford Cryosystems Cryostream cooling apparatus. 5.11°<θ<25.02°; 9463 measured reflections. 5577 independent (Rint, 0.03, 3287 with 1>3σ(I, The structure was solved by direct methods by using the program SIR92 reference [57, and refined by full-matrix least-squares procedure on F. Graphical calculations we
    • -3. The non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were located in Fourier maps and their positions adjusted geometrically (after each cycle of refinement) with isotropic thermal parameters. One hydroxyl group was modelled as disordered over two positions (O(101)-H-(401) and O(102)-H(402)) with refined occupancies. A Chebychev weighting scheme was applied (reference [60]).
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    • and references therein
    • B. H. Lipshutz, Synlett 1990, 119, and references therein.
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    • 84921424899 scopus 로고    scopus 로고
    • X-ray crystallographic structure determination of, )-38: Crystal data: Empirical Formula: C27H36BrClO2Si; Mw =536.01; colourless block 0.18×0.18×0.09mm 3; monoclinic P21 (no. 4, a, 10.8644(5, b, 9.8760(4, c, 13.4194(6) Å; β=110.439(2)°: V, 1349.2(2) Å3; Z, 2; T=180(2)°K; DX= 1.319g cm-3; λ= 0.71073 Å: μ, 1.688 mm-1; Nonius Kappa CCD diffractometer equipped with an Oxford Cryosystems Cryostream cooling apparatus; 3.63°<θ< 27.45°; 8801 measured reflections, 5659 independent (Rint =0.039, 4628 with I>4σ(I, The structure was solved by direct methods (SHELXS-97. reference [31, and refined by least squares SHELXL-97, reference [31, by using Chebyshev weights on Fo2 t
    • 2= 1.044: residual electron density = 0.26 eÅ-3,
  • 98
    • 33847637959 scopus 로고    scopus 로고
    • For a recent rationalisation regarding the outcome of halogenation reactions on eight-membered ethers see: H. Kim, H. Lee, D. Lee, S. Kim, D. Kim, J. Am. Chem. Soc. 2007, 129, 2269
    • For a recent rationalisation regarding the outcome of halogenation reactions on eight-membered ethers see: H. Kim, H. Lee, D. Lee, S. Kim, D. Kim, J. Am. Chem. Soc. 2007, 129, 2269.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.