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Volumn 46, Issue 31, 2007, Pages 5916-5920

Synthesis, biosynthesis, and absolute configuration of vioxanthin

Author keywords

Biaryls; Circular dichroism; Michael addition; Phenol coupling; Polyketides

Indexed keywords

MICHAEL ADDITION; PHENOL COUPLING; POLYKETIDES;

EID: 34547804840     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200701014     Document Type: Article
Times cited : (55)

References (40)
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    • In plants (Forsythia suspensa), diligent proteins have been found to be crucial for the regio- and stereoselective phenol coupling of lignans: L. B. Davin, H.-B. Wang, A. Crowell, D. L. Bedgar, D. M. Martin, S. Sarkanen, N. G. Lewis, Science 1997, 275, 362-366.
    • In plants (Forsythia suspensa), diligent proteins have been found to be crucial for the regio- and stereoselective phenol coupling of lignans: L. B. Davin, H.-B. Wang, A. Crowell, D. L. Bedgar, D. M. Martin, S. Sarkanen, N. G. Lewis, Science 1997, 275, 362-366.
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    • Cross-coupling for regioselective coupling of two aryls: a for a review, see: J. Hassan, M. Sévignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev. 2002, 102, 1359-1469;
    • Cross-coupling for regioselective coupling of two aryls: a) for a review, see: J. Hassan, M. Sévignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev. 2002, 102, 1359-1469;
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    • Asymmetric coupling of two aryl units: a for a review, see: M. P. Sibi, S. Manyem, J. Zimmerman, Chem. Rev. 2003, 103, 3263-3295;
    • Asymmetric coupling of two aryl units: a) for a review, see: M. P. Sibi, S. Manyem, J. Zimmerman, Chem. Rev. 2003, 103, 3263-3295;
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    • The descriptor (aS) used by Zeeck et al. (reference [6]) is equivalent to P. Herein, the M/P rather than the aR/aS description is used: G. Helmchen, Methods of Organic Chemistry (Houben-Weyl), E21a (Ed.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, p. 1-74.
    • The descriptor (aS) used by Zeeck et al. (reference [6]) is equivalent to P. Herein, the M/P rather than the aR/aS description is used: G. Helmchen, Methods of Organic Chemistry (Houben-Weyl), Vol. E21a (Ed.: G. Helmchen, R. W. Hoffmann, J. Mulzer, E. Schaumann), Thieme, Stuttgart, 1995, p. 1-74.
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    • Up to now rubrosulphin has not been isolated as a metabolite from Penicillium citreoviride. Rubrosulphin has been isolated from Aspergillus sulphureus, A. melleus, and P. viridicatum: a R. C. Durley, J. MacMillan, T. J. Simpson, A. Glen, W. B. Turner, J. Chem. Soc. Perkin Trans. 1 1975, 163-167;
    • Up to now rubrosulphin has not been isolated as a metabolite from Penicillium citreoviride. Rubrosulphin has been isolated from Aspergillus sulphureus, A. melleus, and P. viridicatum: a) R. C. Durley, J. MacMillan, T. J. Simpson, A. Glen, W. B. Turner, J. Chem. Soc. Perkin Trans. 1 1975, 163-167;
  • 26
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    • 7-O-Desmethyl semivioxanthin (4) has been isolated from Penicillium janthineltum: A. E. de Jesus, P. S. Steyn, F. R. van Heerden, S. Afr. J. Chem. 1983, 36, 82-83
    • 7-O-Desmethyl semivioxanthin (4) has been isolated from Penicillium janthineltum: A. E. de Jesus, P. S. Steyn, F. R. van Heerden, S. Afr. J. Chem. 1983, 36, 82-83.
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    • Originally, racemic 7-O-desmethyl semivioxanthin (rac-[10-13C]4) 13C labeled at C10 was synthesized by a similar route to semivioxanthin (2) synthesis. The 13C label was introduced by 13CO2 addition to 2,6-dimethoxy-4-methylbromobenzene. Feeding experiments with rac-[10-13C]4 as the substrate revealed incorporation into metabolites 1 and 2, but by 13C NMR spectroscopy only one signal heightened for C10, C10′ was observed in the putatively diastereomeric vioxanthin products. Thus, no conclusion regarding the detection of the three diastereomers was possible. Therefore, a 1:1 mixture of (R, 1-13C]4 (8mg) and (S, 1- 13C]4 (8 mg) was used for a feeding experiment with racemic [1-13C]4
    • 13C]4.
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    • Exciton Chirality Method: Principles and Applications: N. Berova, K. Nakanishi in Circular Dichroism, Principles and Applications, 2nd ed. (Eds.: N. Berova, K. Nakanishi, R. W. Woody), Wiley-VCH, New York, 2000, pp. 337-382.
    • b) "Exciton Chirality Method: Principles and Applications": N. Berova, K. Nakanishi in Circular Dichroism, Principles and Applications, 2nd ed. (Eds.: N. Berova, K. Nakanishi, R. W. Woody), Wiley-VCH, New York, 2000, pp. 337-382.
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    • [17] In a comparable annelation with stabilized dianions, Hauser and Gauuan obtained a bisanthraquinone in 23% yield: F. M. Hauser, P. J. F. Gauuan, Org. Lett. 1999, 1, 671-672.
    • [17] In a comparable annelation with stabilized dianions, Hauser and Gauuan obtained a bisanthraquinone in 23% yield: F. M. Hauser, P. J. F. Gauuan, Org. Lett. 1999, 1, 671-672.
  • 36
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    • 3 in the reaction mixture should be in the range of 30-35 mM.
    • 3 in the reaction mixture should be in the range of 30-35 mM.
  • 37
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    • 2O can be found in the literature: G. A. Kraus, X. Wang, Tetrahedron Lett. 1999, 40, 8513-8514.
    • 2O can be found in the literature: G. A. Kraus, X. Wang, Tetrahedron Lett. 1999, 40, 8513-8514.
  • 40
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    • 13C NMR spectra with two carbonyl signals at δ = 171.61 ppm and δ = 171.57 ppm. Although the correct P,R,R configuration for natural vioxanthin (1) from P. citreoviride has been proposed by Zeeck et al. (reference [7]), their approach to confirm this is not valid: The CD spectra of 1 in the range of 300-450 nm is not predominantly determined by the chirality of the stereogenic centers, but rather by the axial chirality.
    • 13C NMR spectra with two carbonyl signals at δ = 171.61 ppm and δ = 171.57 ppm. Although the correct P,R,R configuration for natural vioxanthin (1) from P. citreoviride has been proposed by Zeeck et al. (reference [7]), their approach to confirm this is not valid: The CD spectra of 1 in the range of 300-450 nm is not predominantly determined by the chirality of the stereogenic centers, but rather by the axial chirality.


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