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Volumn 46, Issue 36, 2007, Pages 6870-6873

Access to guaianolides: Highly efficient stereocontrolled total synthesis of (±)-geigerin

Author keywords

Conjugate addition; Cycloaddition; Guaianolides natural products; Total synthesis

Indexed keywords

CYCLOADDITION; POSITIVE IONS; REGIOSELECTIVITY; SYNTHESIS (CHEMICAL);

EID: 34548726167     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200702031     Document Type: Article
Times cited : (32)

References (53)
  • 6
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    • no further references to vermimeeric acid appear in electronic reference searches
    • c) no further references to vermimeeric acid appear in electronic reference searches.
  • 12
    • 34548777887 scopus 로고    scopus 로고
    • Ideal synthesis: P. A. Wender, S. T. Handy, D. L. Wright, Chem. Ind. 1997, 19, 765.
    • Ideal synthesis: P. A. Wender, S. T. Handy, D. L. Wright, Chem. Ind. 1997, 19, 765.
  • 14
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    • Step economy: a P. A. Wender, J. L. Bariza, S. E. Brener, M. O. Clarke, G. G. Gamber, J. C. Horan, T. C. Jessop, C. Kan, K. Pattabiraman, T. J. Williams, Pure Appl. Chem. 2003, 75, 143, and references therein;
    • Step economy: a) P. A. Wender, J. L. Bariza, S. E. Brener, M. O. Clarke, G. G. Gamber, J. C. Horan, T. C. Jessop, C. Kan, K. Pattabiraman, T. J. Williams, Pure Appl. Chem. 2003, 75, 143, and references therein;
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    • Atom economy: a B. M. Trost, Science 1991, 254, 1471;
    • Atom economy: a) B. M. Trost, Science 1991, 254, 1471;
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    • Eds, L. F. Tietze, G. Brasche, K. M. Gericke, Wiley-VCH, Weinheim
    • d) Domino Reactions in Organic Synthesis (Eds.: L. F. Tietze, G. Brasche, K. M. Gericke), Wiley-VCH, Weinheim, 2006.
    • (2006) Domino Reactions in Organic Synthesis
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    • For a special issue on environmental chemistry, see: Chem. Rev. 1995, 95, 3.
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    • Angew. Chem. Int. Ed. 2005, 44, 5130.
    • (2005) Chem. Int. Ed , vol.44 , pp. 5130
    • Angew1
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    • Tropylium ion can be obtained easily on a large scale (50-100 g) in 80 % yield from cycloheptatriene (dichloroethane can be used to replace toxic carbon tetrachloride). See: K. Conrow, Org. Synth. Coll., V, Wiley, New York, 1973, p. 1138.
    • Tropylium ion can be obtained easily on a large scale (50-100 g) in 80 % yield from cycloheptatriene (dichloroethane can be used to replace toxic carbon tetrachloride). See: K. Conrow, Org. Synth. Coll., Vol. V, Wiley, New York, 1973, p. 1138.
  • 28
    • 34548805253 scopus 로고    scopus 로고
    • The dichloroketene cycloaddition reaction can be performed more easily by using zinc powder under ultrasonic irradiation instead of activated zinc (Zn-Cu) and POCl3 with stirring. See: J.-P. Deprés in Synthetic Organic Sonochemistry Ed, J.-L. Luche, Plenum, New York, 1998, p. 345
    • 3 with stirring. See: J.-P. Deprés in Synthetic Organic Sonochemistry (Ed.: J.-L. Luche), Plenum, New York, 1998, p. 345.
  • 32
    • 34548769605 scopus 로고    scopus 로고
    • This conjugate addition reaction is more stereoselective than with the methyl silyl ketene acetal in the presence of TiCl4. The opposite behavior is observed with LiClO4
    • 4.
  • 34
  • 35
    • 34548720120 scopus 로고    scopus 로고
    • 3) at room temperature. From the corresponding methyl ester, the yield is lower and a reaction time of three days is necessary.
    • 3) at room temperature. From the corresponding methyl ester, the yield is lower and a reaction time of three days is necessary.
  • 36
    • 34548782470 scopus 로고    scopus 로고
    • The C11 epimer can be converted to 6-deoxygeigerin (3) with KOH in ethanol. See Refs. [12a] and [3c].
    • The C11 epimer can be converted to 6-deoxygeigerin (3) with KOH in ethanol. See Refs. [12a] and [3c].
  • 38
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    • 4, see: a P. A. Grieco, R. J. Cooke, K. J. Henry, J. M. VanderRoest, Tetrahedron Lett. 1991, 32, 4665;
    • 4, see: a) P. A. Grieco, R. J. Cooke, K. J. Henry, J. M. VanderRoest, Tetrahedron Lett. 1991, 32, 4665;
  • 40
    • 34548726566 scopus 로고    scopus 로고
    • The silyl ketene acetal E/Z configurational effect in the 1,6-conjugate addition will be studied in detail in the near future.
    • The silyl ketene acetal E/Z configurational effect in the 1,6-conjugate addition will be studied in detail in the near future.
  • 48
    • 34548752086 scopus 로고    scopus 로고
    • The expected relative stereochemistry of the hydroxyl at C6 (α isomer) was confirmed by X-ray diffraction analysis of 1. Crystallographic data for 1 (C15H20O4, monoclinic, space group P21, a, 18.927(5, b, 7.956(3, c, 20.555(3) Å, β, 113.79(2)°, V, 2832(2)Å3, Z, 4, ρcalcd, 1.24 Mgm -3, 2θmax, 75°, MoKα radiation (λ, 1.54178 Å, T= 293 K, 5808 independent reflections, 2940 reflections used with I > 2.0σ, diffractometer: CAD4-Enraf-Nonius. CCDC-636014 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre www.ccdc.cam.ac.uk/data_request/cif
    • Kα radiation (λ = 1.54178 Å), T= 293 K, 5808 independent reflections, 2940 reflections used with I > 2.0σ, diffractometer: CAD4-Enraf-Nonius. CCDC-636014 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre (www.ccdc.cam.ac.uk/data_request/cif).
  • 49
    • 34548750699 scopus 로고    scopus 로고
    • When the first two reactions are conducted in one pot, the yield is 44, from 6
    • When the first two reactions are conducted in one pot, the yield is 44 % from 6.
  • 53
    • 34548788824 scopus 로고    scopus 로고
    • This stereoselective 1,4-conjugate addition is currently under study; preliminary results show that the reaction is possible and introduces the desired β methyl group at C5
    • This stereoselective 1,4-conjugate addition is currently under study; preliminary results show that the reaction is possible and introduces the desired β methyl group at C5.


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