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This assignment is based, in part, on the fact that the alternate oxazoline would suffer from severe steric interactions with the protons from the C-11 position in ring F. Such strain also renders the approach of DAST or any other reagent from that side of the molecule quite unlikely.
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44
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4043178591
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4 at 25 °C and reflux.
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The scope of this new protocol is explored more fully in the final article in this series and has proven applicable to the formation of diverse oxazoles from ketoamides, thiazolines from thioamide-alcohols, thiazoles from ketothioamides, and furans from 1,4-dicarbonyls.
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52
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The same operation could also be accomplished in slightly lower yield using TBAF. For an application of this alternative protocol in total synthesis, see: Jiang, W.; Wanner, J.; Lee, R. J.; Bounard, P.-Y.; Boger, D. L. J. Am. Chem. Soc. 2002, 124, 5288-5290.
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To achieve such a smooth rearrangement at a low temperature typically requires the presence of a protic or Lewis acid; in this case, the particular spatial arrangement of the reactive groups in 17 must facilitate this conversion as no such activators were needed.
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58
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For other syntheses which benefited from this reagent combination, see: (a) Nicolaou, K. C.; Koumbis, A. E.; Takayanagi, M.; Natarajan, S.; Jain, N. F.; Bando, T.; Li, H.; Hughes, R. Chem. Eur. J. 1999, 5, 2622-2647.
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0035905365
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2/HMPA-based hetero-pinacol sequence in this model system versus the fully functionalized intermediates presented in Scheme 8.
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