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0013122191
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note
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However, in some fumagillin analogs, which displayed in vivo antitumor activity, the spiro epoxide is transformed into a hydroxy methylenesulfonium derivative, see ref. 7a.
-
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25
-
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0013166807
-
-
note
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For clarity, the fumagillin numbering has systematically been used.
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27
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0037041597
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0030200756
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For recent accounts of Claisen-Ireland rearrangements, see: (a) Y. Chai, S-p. Hong, H. A. Lindsay, C. McFarland, M. C. McIntosh. Tetrahedron 58, 2905 (2002); (b) D. Enders, M. Knopp, R. Schiffers. Tetrahedron: Asymmetry 7, 1847 (1996); (c) J. S. Panek, S. Schaus, C. E. Masse. Chemtracts: Org. Chem. 8, 238 (1995).
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0013124338
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note
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Alternatively, it was possible to prepare an enantiomeric lactone of 22 with an E-double bond on side chain. Rearrangement of this lactone could give rise to a diastereomer of 27 with natural configuration at C4 and unnatural at C3. Inversion of configuration at C3 as in previous syntheses could then be realized. However, the lengthy preparation of lactone 22 [26] was a major drawback for the use of this alternative.
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31
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Minor diastereomers were eliminated at this stage during ester purification.
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