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Compound 3 is the major fatty acid substructure in malyngamides; for a review, see reference [1]; a L. T. Tan, T. Okino, W. H. Gerwick, J. Nat. Prod. 2000, 63, 952-955;
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Compound 3 is the major fatty acid substructure in malyngamides; for a review, see reference [1]; a) L. T. Tan, T. Okino, W. H. Gerwick, J. Nat. Prod. 2000, 63, 952-955;
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The tripeptide moiety 1 was numbered with respect to the neurotoxin janolusimide (6), a very similar tripeptide; a) G. Sodano, A. Spinella, Tetrahedron Lett. 1986, 27, 2505-2508;
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The tripeptide moiety 1 was numbered with respect to the neurotoxin janolusimide (6), a very similar tripeptide; a) G. Sodano, A. Spinella, Tetrahedron Lett. 1986, 27, 2505-2508;
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3- pyrrolin-2-one, see: B. J. L. Royles, Chem. Rev. 1995, 95, 1981-2001.
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3- pyrrolin-2-one, see: B. J. L. Royles, Chem. Rev. 1995, 95, 1981-2001.
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H,H = 0-4 Hz); a) C. H. Heathcock, M. C. Pirrung, J. E. Sohn, J. Org. Chem. 1979, 44, 4294-4299;
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H,H = 0-4 Hz); a) C. H. Heathcock, M. C. Pirrung, J. E. Sohn, J. Org. Chem. 1979, 44, 4294-4299;
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b) S. Paik, S. Carmeli, J. Cullingham, R. E. Moore, G. M. L. Patterson, M. A. Tius, J. Am. Chem. Soc. 1994, 116, 8116-8125.
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22
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0033525048
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H,H is a value typical for an anti configuration, the NOE analysis should be reliable, as no significant conformational change takes place; N. Matsumori, D. Kaneno, M. Murata, H. Nakamura, K. Tachibana, J. Org. Chem. 1999, 64, 866-876. (Chemical Equation Presented)
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H,H is a value typical for an anti configuration, the NOE analysis should be reliable, as no significant conformational change takes place; N. Matsumori, D. Kaneno, M. Murata, H. Nakamura, K. Tachibana, J. Org. Chem. 1999, 64, 866-876. (Chemical Equation Presented)
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I. Ohtani, T. Kusumi, Y. Kashman, H. Kakisawa, J. Am. Chem. Soc. 1991, 113, 4092-4096.
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Ohtani, I.1
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24
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0001123933
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The method pioneered by Pirkle and Beare follows from the possibility of relating the sense of chemical shift nonequivalence (upfield vs. downfield of a signal) for one enantiomer of a compound dissolved in an optically active solvent; see, for instance: a) W. H. Pirkle, S. D. Beare, J. Am. Chem. Soc. 1969, 91, 5150-5155;
-
The method pioneered by Pirkle and Beare follows from the possibility of relating the sense of chemical shift nonequivalence (upfield vs. downfield of a signal) for one enantiomer of a compound dissolved in an optically active solvent; see, for instance: a) W. H. Pirkle, S. D. Beare, J. Am. Chem. Soc. 1969, 91, 5150-5155;
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c) D. Parker, Chem. Rev. 1991, 91, 1441-1457;
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There are very few reports about the use of CSAs for absolute configuration assignment; a S. Latypov, X. Franck, J.-C. Jullian, R. Hocquemiller, B. Figadére, Chem. Eur. J. 2002, 8, 5662-5666;
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There are very few reports about the use of CSAs for absolute configuration assignment; a) S. Latypov, X. Franck, J.-C. Jullian, R. Hocquemiller, B. Figadére, Chem. Eur. J. 2002, 8, 5662-5666;
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31
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33846322662
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The interaction between TFAE and the substrate was not as strong as the covalent bond of the MTPA ester in the modified Mosher method. The observed ΔδRS values were thus the average shifts of the signals of the diastereomeric complexes that rapidly equilibrate with the bulk of cosolvent on the NMR timescale
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RS values were thus the average shifts of the signals of the diastereomeric complexes that rapidly equilibrate with the bulk of cosolvent on the NMR timescale.
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32
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0033593395
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K. Akaji, Y. Hayashi, Y. Kiso, N. Kuriyama, J. Org. Chem. 1999, 64, 405-411.
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33
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33846282022
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For absolute configuration assignment with aid from conformational calculations, see, for example: a
-
For absolute configuration assignment with aid from conformational calculations, see, for example: a) M. Ubutaka, X.-C. Cheng, M. Isobe, K. Isono, J. Chem. Soc. Perkin Trans. 1 1993, 617-624;
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Luesch, H.1
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0037111707
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c) R. T. Williamson, A. Boulanger, A. Vulpanovici, M. A. Roberts, W. H. Gerwick, J. Org. Chem. 2002, 67, 7927-7936;
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37
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33846321979
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3 and 8-H.
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3 and 8-H.
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-
38
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0031909145
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The biosynthetic considerations have recently been employed to solve the stereochemistry of C7′; see: Y. Kan, T. Fujita, H. Nagai, B. Sakamoto, Y. Hokama, J. Nat. Prod. 1998, 61, 152-155, and reference [7].
-
The biosynthetic considerations have recently been employed to solve the stereochemistry of C7′; see: Y. Kan, T. Fujita, H. Nagai, B. Sakamoto, Y. Hokama, J. Nat. Prod. 1998, 61, 152-155, and reference [7].
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39
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33846282120
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We recently completed the total synthesis of (7′R)-1. The specific rotation of natural 1, α]D, 6.2 (c, 0.8, MeOH, matched that of (7′R)-1, α]D, 5.9 (c, 0.8, MeOH, but differed from that of (7′S)-1, α]D, 15.4 (c, 0.8, MeOH, This difference must be due to the large distance between the C7′ stereogenic center and the other five stereogenic centers in the tripeptide portion. The consistent result in the NMR chiral solvation experiments was obtained with synthetic (7′R)-1. The details for the total synthesis of both (7′R, and (7′S)-malyngamide X and the NMR chiral solvation experiments will be reported elsewhere
-
D = -15.4 (c = 0.8, MeOH). This difference must be due to the large distance between the C7′ stereogenic center and the other five stereogenic centers in the tripeptide portion. The consistent result in the NMR chiral solvation experiments was obtained with synthetic (7′R)-1. The details for the total synthesis of both (7′R)- and (7′S)-malyngamide X and the NMR chiral solvation experiments will be reported elsewhere.
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40
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42
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33846306088
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D measurements.
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D measurements.
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0018606732
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Boyd, M.R.10
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