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It is worth noting that the acetyl protection in 11 was critical since installation of electron-donating groups at C-7 hydroxyl causes 11 to collapse into stable epoxide derivatives.
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The experimental conditions capitalized on the findings previously reported by Helm and Li (excess cesium 2-methoxyphenolate, 18-crown-6, benzene, reflux, 24 h; ref 14d).
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44
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33750430479
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On the basis of our results, the absolute configuration of levorotatory virolin in ref 15a should be reverted (7R,8R).
-
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46
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3, 18-crown-6 in DMF, sonication) as compared to the previous microwave-assisted substitution procedure (see text) since it is known that the presence of a carboxylate or a carbonyl group adjacent to the alcohol (or bromine) function strongly activates the substrate for nucleophilic displacement. See, for example, ref 16a.
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Overall, these findings indirectly confirmed a (7R,8R)-configuration for the minor syn-configured products, whose structures coincide with those of compounds (-)-1, (-)-2, and (-)-3.
-
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50
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33750429463
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13C chemical shift assignments follow the conventional 8,4′-oxyneolignan numbering. See ref 2.
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