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0142181514
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This applies to all 13 individual fattiviracins known to date, cf. refs 2 and 5.
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0142243659
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The order of silylation and hydrogenation can also be inversed. In this case, however, the overall yield of product 6 is somewhat lower due to partial cleavage of the terminal TBDPS group during the asymmetric reduction step.
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0032958497
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Although the closely related shift values of the glucokinase activating macrodiolide glucolipsin A seem to suggest that this particular compound which contains ah extra methyl branch at the adjacent position - might also be (3R,3′R) configured, a recent total synthesis by our group shows that glucolipsin incorporates in fact a (2R,3S)-configured syn aldol entity. For the isolation of glucolipsin, see: Qian-Cutrone, J.; Ueki, T.; Huang, S.; Mookhtiar, K. A.; Ezekiel, R.; Kalinowski, S. S.; Brown, K. S.; Golik, J.; Lowe, S.; Pirnik, D. M.; Hugill, R.; Veitch, J. A.; Klohr, S. E.; Whitney, J. L.; Manly, S. P. J. Antibiot. 1999, 52, 245. (diagram presented)
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0142150532
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note
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The synthesis of this compound is outlined in the Supporting Information.
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74
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0142150531
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note
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1H NMR spectra which are also distinctly different for the pairs of stereoisomers 31/33, 42/43, 44/45. Particularly diagnostic is the shift of the terminal methyl group of the fatty acid chain which resonates at Δ = 1.34 ppm in the 17S-configured compounds but at Δ = 1.31 ppm in the 17R-configured products. The pertinent shift in the natural product is Δ = 1.34 ppm.
-
-
-
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75
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0142243655
-
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note
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If the fatty acids are drawn in a zigzag conformation, all hydroxyl groups are located on the same side; the fact that the centers at C-17' and C-19 are S-configured while the other ones are R-configured simply reflects the formalism of the Cahn - Ingold-Prelog nomenclature.
-
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76
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0142150530
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note
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Note again the formalism of the Chan-Ingold-Prelog nomenclature. The use of the (2R)-configured aldehyde 58 will ultimately result in a (19S)-configured cycloviracin derivative due to change in priorities of the substituents at that center.
-
-
-
-
80
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84969808662
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