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Volumn 75, Issue 15, 2010, Pages 4929-4938

Development of an enantioselective route toward the lycopodium alkaloids: Total synthesis of lycopodine

Author keywords

[No Author keywords available]

Indexed keywords

ENANTIOSELECTIVE; ENANTIOSELECTIVE TOTAL SYNTHESIS; INTRAMOLECULAR MICHAEL ADDITION; NATURAL PRODUCTS; ORGANOCATALYSTS; ORGANOCATALYTIC; RING SYSTEMS; SYNTHETIC SEQUENCE; TOTAL SYNTHESIS;

EID: 77955145874     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo100916x     Document Type: Article
Times cited : (70)

References (107)
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    • For a recent review of organocatalysis on sulfone substrates, see:;;, - 2033
    • For a recent review of organocatalysis on sulfone substrates, see: Alba, A.-N. R.; Companyó, X.; Rios, R. Chem. Soc. Rev. 2010, 39, 2018 - 2033.
    • (2010) Chem. Soc. Rev. , vol.39 , pp. 2018
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    • For a recent review of ee determination using NMR methods, see
    • For a recent review of ee determination using NMR methods, see: Seco, J. M.; Quinoa, E.; Riguera, R. Chem. Rev. 2004, 104, 17-118
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    • Seco, J.M.1    Quinoa, E.2    Riguera, R.3
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    • 25 alkyl chain. No attempt was made to separate the isomers in this sequence, and the isomeric mixture does not appear to adversely affect the reactivity
    • 25 alkyl chain. No attempt was made to separate the isomers in this sequence, and the isomeric mixture does not appear to adversely affect the reactivity.
  • 76
    • 84855626099 scopus 로고    scopus 로고
    • This crystal structure was determined using the ent - 31 catalyst derived from d -proline. CCDC-663,290 (ent- 25) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via
    • This crystal structure was determined using the ent-31 catalyst derived from d -proline. CCDC-663,290 (ent- 25) contains 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.
  • 77
    • 84855627055 scopus 로고    scopus 로고
    • CCDC-663,289 (37) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • CCDC-663,289 (37) contains 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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    • 1842739384 scopus 로고    scopus 로고
    • For palladium-catalyzed methods, see:;;, and references cited therein
    • For palladium-catalyzed methods, see: Jagusch, T.; Gais, H.-J.; Bondarev, O. J. Org. Chem. 2004, 69, 2731-2736 and references cited therein
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    • Jagusch, T.1    Gais, H.-J.2    Bondarev, O.3
  • 83
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    • Absolute and relative configuration of product 39e were assigned based on analogy to the 6-membered series
    • Absolute and relative configuration of product 39e were assigned based on analogy to the 6-membered series.
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    • 84855627053 scopus 로고    scopus 로고
    • 15 methyl series appears to perform slightly better in the CM than the desmethyl series. We are unsure as to the exact explanation for that difference
    • 15 methyl series appears to perform slightly better in the CM than the desmethyl series. We are unsure as to the exact explanation for that difference.
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    • 84855626390 scopus 로고    scopus 로고
    • The CIF containing the supplementary crystallographic data for compound 7 has been previously reported. These data can be obtained free of charge from the American Chemical Society via
    • The CIF containing the supplementary crystallographic data for compound 7 has been previously reported. These data can be obtained free of charge from the American Chemical Society via http://pubs.acs.org/doi/suppl/10.1021/ ja803613w/suppl-file/ja803613w-file006.cif.
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    • Attempts to switch the diastereoselectivity of this reaction through the use of sulfonamide catalyst 31 conditions led to a formation the same diastereomer 7; however, use of enantiomeric sulfamide catalyst ent - 31 gave what we have tentatively assigned as the alternate trans -disatereomer 48 in modest diastereosectivity (1.5:1 dr)
    • Attempts to switch the diastereoselectivity of this reaction through the use of sulfonamide catalyst 31 conditions led to a formation the same diastereomer 7; however, use of enantiomeric sulfamide catalyst ent-31 gave what we have tentatively assigned as the alternate trans -disatereomer 48 in modest diastereosectivity (1.5:1 dr).
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    • 84855626386 scopus 로고    scopus 로고
    • The CIF containing the supplementary crystallographic data for compound 49 has been previously reported. These data can be obtained free of charge from the American Chemical Society via
    • The CIF containing the supplementary crystallographic data for compound 49 has been previously reported. These data can be obtained free of charge from the American Chemical Society via http://pubs.acs.org/doi/suppl/10.1021/ ja803613w/suppl-file/ja803613w-file007.cif.
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    • One example of such a [2,3]-sigmatropic rearrangement has been reported
    • One example of such a [2,3]-sigmatropic rearrangement has been reported: Hatanaka, N.; Ozaki, O.; Matsumoto, M. Tetrahedron Lett. 1986, 27, 3169-3172
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    • Preparation of LiTMP: To a solution of 2,2,6,6-tetramethylpiperidine (283 mg, 340 μL, 2.0 mmol) in THF (0.86 mL) was added n -BuLi (0.8 mL, 2.0 mmol, 2.5 M in hexanes). The reaction was warmed to -10 °C and stirred for 30 min prior to use
    • Preparation of LiTMP: To a solution of 2,2,6,6-tetramethylpiperidine (283 mg, 340 μL, 2.0 mmol) in THF (0.86 mL) was added n -BuLi (0.8 mL, 2.0 mmol, 2.5 M in hexanes). The reaction was warmed to -10 °C and stirred for 30 min prior to use.


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