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0142050792
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The enantiomer of 9 was used. see ref 15
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The enantiomer of 9 was used. see ref 15.
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49
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3.
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52
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0142082627
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note
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Use of tributylphosphine as the reducing agent minimized methanolysis of the acetal in this step.
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53
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3, pyridine; IBX; PDC; TPAP, NMO; Dess-Martin, pyridine.
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57
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The oxidation of diketones by iodine-III species is a well-known process, see for a review: Moriarty, R. M.; Prakash, O. Org. React. 1999, 54, 273. We have also isolated the triketone product in a similar system: Claffey, M. M.; Heathcock, C. H., unpublished results.
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note
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See the Supporting Information for the reactions used and yields obtained in the preparation of 19 and 22.
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note
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Care had to be taken to avoid overreduction to the alkane; TLC analysis with 30% ethyl acetate in benzene separates the alkene from the overreduced product.
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note
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Recall that our first-generation spiroketalization substrate had one more carbon in the chain, making the TBS ether in that case significantly less sterically hindered.
-
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70
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0142114108
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-
note
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Migration of the pivaloyl protecting group to the secondary alcohol was observed during the epoxide opening when the more direct route from glycidol pivalate was attempted.
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note
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3 and MeI did not effect the desired reaction so NaH was added to the reaction mixture.
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74
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0003536850
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0142018848
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note
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The same stereoelectronic preference operates in the formation of the A/ B spiroketal 18 (Scheme 4). In that case, axial addition of the C11 hydroxy group should give the observed S spiroketal because addition should be trans to the substituent at C3. which in this case has the R configuration.
-
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82
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0028912353
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For examples in which proximal heteroatom substituents stabilize glycosides with respect to acid-catalyzed hydrolysis, see: (a) Roush, W. R.; Lin, X.-F. J. Am. Chem. Soc. 1995, 117, 2236.
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