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Volumn 46, Issue 10, 2007, Pages 1634-1637

Oxidative cleavage of 3-alkoxy-2,5-dihydrofurans and its application to the de novo synthesis of rare monosaccharides as exemplified by L-cymarose

Author keywords

Allenes; Carbohydrates; Oxidation; Oxygen heterocycles; Reduction

Indexed keywords

ALDEHYDES; OXIDATION; SYNTHESIS (CHEMICAL);

EID: 34248171085     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200604078     Document Type: Article
Times cited : (43)

References (50)
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    • selected examples of the application of alkoxyallenes to natural product synthesis: c) G. Stork, E. Nakamura, J. Am. Chem. Soc. 1983, 105, 5510-5512;
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    • Synthesis of 3-methoxy-2-methylfuran: C. Meister, H.-D. Scharf, Synthesis 1981, 737-739.
    • Synthesis of 3-methoxy-2-methylfuran: C. Meister, H.-D. Scharf, Synthesis 1981, 737-739.
  • 19
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    • 5 has transient character. When only one equivalent of DDQ is used in the oxidation, keto aldehyde 6 and dihydrofuran 4 are isolated in equal proportions. Attempts to trap species 5 in situ in the presence of various dienophiles were unsuccessful;
    • a) 5 has transient character. When only one equivalent of DDQ is used in the oxidation, keto aldehyde 6 and dihydrofuran 4 are isolated in equal proportions. Attempts to trap species 5 in situ in the presence of various dienophiles were unsuccessful;
  • 20
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    • the oxidative cleavage of 3-methoxy-2,5-diphenylfuran with DDQ has been described: S. Sayama, Y. Inamura, Heterocycles 1996, 43, 1371-1374.
    • b) the oxidative cleavage of 3-methoxy-2,5-diphenylfuran with DDQ has been described: S. Sayama, Y. Inamura, Heterocycles 1996, 43, 1371-1374.
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    • 2 at reflux failed to aromatize substrates 4. Oxidation of 4a with three equivalents of pyridinium chlorochromate (PCC) in pyridine/dichloromethane gave 15 % 6a along with 11 % of the highly unstable corresponding furan.
    • 2 at reflux failed to aromatize substrates 4. Oxidation of 4a with three equivalents of pyridinium chlorochromate (PCC) in pyridine/dichloromethane gave 15 % 6a along with 11 % of the highly unstable corresponding furan.
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    • I-catalyzed cycloisomerizations of alkynes to furans proceeding via allene intermediates: R. C. D. Brown, Angew. Chem. 2005, 117, 872-874;
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    • This method requires four equivalents of DDQ because of partial inactivation of the reagent
    • This method requires four equivalents of DDQ because of partial inactivation of the reagent.
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    • The cleavage of furan derivatives with PCC has been described and probably proceeds by a [4+3] cycloaddition of the chromium reagent with the furan followed by cycloreversion: a G. Piancatelli, A. Scettri, M. D'Auria, Tetrahedron Lett. 1977, 2199-2200;
    • The cleavage of furan derivatives with PCC has been described and probably proceeds by a [4+3] cycloaddition of the chromium reagent with the furan followed by cycloreversion: a) G. Piancatelli, A. Scettri, M. D'Auria, Tetrahedron Lett. 1977, 2199-2200;
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    • III: c) A. Hoffmann-Röder, N. Krause, Org. Lett. 2001, 3, 2537-2538.
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    • Isolation of heliquinomycin: a M. Chino, K. Nishikawa, M. Umekita, C. Hayashi, T. Yamazaki, T. Tsuchida, T. Sawa, M. Hamada, T. Takeuchi, J. Antibiot. 1996, 49, 752-757;
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    • syntheses of several building blocks for heliquinomycin: b) M. Brasholz, H.-U. Reissig, Synlett 2004, 2736-2738;
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    • further examples of cymarose glycosides: the glaucoside family: f T. Nagawa, K. Hayashi, K. Wada, H. Mitsuhashi, Tetrahedron 1983, 39, 606-612;
    • further examples of cymarose glycosides: the glaucoside family: f) T. Nagawa, K. Hayashi, K. Wada, H. Mitsuhashi, Tetrahedron 1983, 39, 606-612;
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    • cynanoside C: h H. Bai, W. Li, K. Koike, T. Satou, Y. Chen, T. Nikaido, Tetrahedron 2005, 61, 5797-5811.
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    • The e.r. value was determined by HPLC on a chiral stationary phase Chiralpak AD, Daicel Chemical Industries Ltd, by comparison with a racemic reference sample
    • The e.r. value was determined by HPLC on a chiral stationary phase (Chiralpak AD, Daicel Chemical Industries Ltd.) by comparison with a racemic reference sample.
  • 47
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    • This represents the shortest stereoselective synthesis of L-cymarose known to date and the only one starting from non-carbohydrate material; known syntheses: a J. S. Brimacombe, R. Hanna, M. S. Saeed, L. C. N. Tucker, J. Chem. Soc. Perkin Trans. 1 1982, 2583-2587, 5 steps starting from methyl 2,3-O-benzylidene-α- L-rhamnopyranoside;
    • This represents the shortest stereoselective synthesis of L-cymarose known to date and the only one starting from non-carbohydrate material; known syntheses: a) J. S. Brimacombe, R. Hanna, M. S. Saeed, L. C. N. Tucker, J. Chem. Soc. Perkin Trans. 1 1982, 2583-2587, 5 steps starting from methyl 2,3-O-benzylidene-α- L-rhamnopyranoside;
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    • Ref. [19], 14 steps starting from methyl α-L- glucopyranoside; synthesis of L-oleandrose with L-cymarose as a side product:
    • b) Ref. [19], 14 steps starting from methyl α-L- glucopyranoside; synthesis of L-oleandrose with L-cymarose as a side product:


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