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Volumn , Issue 4, 2009, Pages 550-553

Thieme Chemistry Journal Awardees - Where are they now? An asymmetric organocatalytic sequence towards 4a-methyl tetrahydroxanthones: Formal synthesis of 4-dehydroxydiversonol

Author keywords

Domino vinylogous aldol oxa Michael reaction; Natural products; Wittig reaction

Indexed keywords


EID: 62249208038     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0028-1087927     Document Type: Article
Times cited : (34)

References (31)
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    • For organocatalytic conjugate addition reactions, see
    • (b) For organocatalytic conjugate addition reactions, see: Almasi, D.; Alonso, D. A.; Najera, C. Tetrahedron: Asymmetry 2007, 18, 299.
    • (2007) Tetrahedron: Asymmetry , vol.18 , pp. 299
    • Almasi, D.1    Alonso, D.A.2    Najera, C.3
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    • The use of salicylaldehyde in domino oxa-Michael reactions for the synthesis of chromenes, coumarins, and related heterocycles has already been reviewed: Shi, Y.-L.; Shi, M. Org. Biomol. Chem. 2007, 5, 1499.
    • (c) The use of salicylaldehyde in domino oxa-Michael reactions for the synthesis of chromenes, coumarins, and related heterocycles has already been reviewed: Shi, Y.-L.; Shi, M. Org. Biomol. Chem. 2007, 5, 1499.
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    • The Trost group used also an asymmetric catalytic approach towards chromanes. The key step is a palladium-catalyzed etherification of phenols with allylic substrates to yield a tetrasubstituted stereogenic center and subsequent ring closure: (a) Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1998, 120, 9074.
    • The Trost group used also an asymmetric catalytic approach towards chromanes. The key step is a palladium-catalyzed etherification of phenols with allylic substrates to yield a tetrasubstituted stereogenic center and subsequent ring closure: (a) Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1998, 120, 9074.
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    • Crystal Structure Study of 4b Single-crystal X-ray diffraction studies were carried out on a Nonius KappaCCD diffractometer at 123(2) K using MoKα radiation (λ, 0.71073 Å, The structures were solved by Direct Methods (SHELXS-9713) and refinement were carried out using SHELXL-9713 (full-matrix least-squares refinement on F2, The hydrogen atoms were localized by difference electron density determination and refined using a 'riding' model (H(O, free, 4b: Colorless crystals, C14H18O4, M, 250.28, crystal size 0.50 x 0.45 x 0.40 mm, triclinic, space group P-1 (No.2, a, 5.9907(2) Å, b, 8.5207(3) Å, c, 12.4965(5) Å, α, 97.603(2)°, β, 95.458(2)°, γ, 97.465(2)°, V, 622.81(4) Å3, Z, 2, ρ(calcd, 1.335 Mg m-3, F000, 268, μ, 0.097 mm
    • -3. Crystallographic data (excluding structure factors) for the structure reported in this work have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 717754 (4b). 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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    • For the hydrogenation of benzylic alcohols, see: a
    • For the hydrogenation of benzylic alcohols, see: (a) Suzuki, M.; Kimura, Y.; Terashima, S. Bull. Chem. Soc. Jpn. 1986, 59, 3559.
    • (1986) Bull. Chem. Soc. Jpn , vol.59 , pp. 3559
    • Suzuki, M.1    Kimura, Y.2    Terashima, S.3
  • 27
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    • Selected NMR Data Compound 4b: 1H NMR (400 MHz, CDCl3, δ, 1.42 (s, 3 H, 1.57 (dd, J, 13.5, 9.8 Hz, 1 H, 1.67 (td, J, 13.5 Hz, 1 H, 2.06-2.14 (m, 2 H, 2.28 (s, 3 H, 3.70 (s, 3 H, 3.86-3.90 (m, 1 H, 4.89 (mc, 1 H, 5.25 (mc, 1 H, 6.13 (s, 1 H, 6.24 (s, 1 H, 13C NMR (100 MHz, CDCl 3, δ, 21.9, 28.6, 34.7, 45.5, 55.4, 61.9, 73.9, 89.9, 102.9, 105.9, 108.5, 140.3, 156.2, 157.1. Compound 9b: 1H NMR (400 MHz, CDCl3, δ, 1.21-1.30 (m, 2 H, 1.28 (t, J, 7.3 Hz, 3 H, 2.04 (s, 3 H, 2.28 (s, 3 H, 2.59 (ddd, J, 14.1, 8.0, 1.3 Hz, 1 H, 2.72 (ddd, J, 14.1, 7.3, 1.3 Hz, 1 H, 3.26 (br s, 1 H, 3.86 (s, 3 H, 4.18 (q, J, 7.3 Hz, 2 H, 4.97 (dd, J, 5.8, 5.3 Hz, 1 H, 5.87 (ddd, J, 15.5, 1.3, 1.3 Hz, 1 H, 6.29 (s, 1 H, 6.35 (s, 1 H, 7.02 ddd, J, 15.5, 7.8, 7.8 Hz, 1 H, 13C NM
    • 3): δ = 18.3, 22.4, 25.5, 30.2, 35.9, 56.1, 78.2, 105.4, 108.2, 108.7, 111.2, 147.1, 160.2, 160.6, 180.3, 182.0.
  • 28
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    • Other Dieckmann condensations generating a 6-6 ring system: (a) Fu, X.; Pechacek, J. T.; Smith, D. L.; Wheeler, D. M. S. Nat. Prod. Lett. 1992, 1, 213.
    • Other Dieckmann condensations generating a 6-6 ring system: (a) Fu, X.; Pechacek, J. T.; Smith, D. L.; Wheeler, D. M. S. Nat. Prod. Lett. 1992, 1, 213.


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