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8
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16
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25
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0345584844
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note
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Structural assignment of the minor diastereomer 10 was supported by the fact that this compound was the only diastereomer generated (dr > 96/4) when the enantiomeric chiral allenylzinc (M)-7 derived from the mesylate (S)-8 was used as the nucleophile in the double-asymmetric condensation with aldehyde 6, which occurs in the matched manifold. The formation of 10 therefore arose from a partial racemization of the allenylmetal reagent during the condensation with aldehyde 6.
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26
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0344722615
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note
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12 Addition of the chiral allenylzinc (P)-7 to aldehyde 6 according to a Felkin-Anh transition state (substrate control) could explain the formation of 11.
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27
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0001359587
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Hafner, A.; Duthaler, R. O.; Marti, R.; Rihs, G.; Rothe-Streit, P.; Schwarzenbach, F. J. Am. Chem. Soc. 1992, 114, 2321.
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Schwarzenbach, F.6
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30
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(b) Frauenrath, H. In Hauben Weyl (Methods of Organic Chemistry), Stereoselective Synthesis; Helmchen, G. Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds.; Thieme-Verlag: Stuttgart, 1995; Vol. E21d, p 3301.
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Frauenrath, H.1
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32
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33749130033
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and references therein
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(b) Enders, D.; Knopp, M.; Runsink, J.; Raabe, G. Angew. Chem, Int. Ed. Engl. 1995, 34, 2278 and references therein.
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34
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35
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0344722612
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note
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16 in which the bulkier branched carbon chain, rather than the methyl group, should preferentially occupy the less congested equatorial position (Scheme 3).
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36
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0345584842
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note
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Carroll rearrangement of the related tertiary allylic β-ketoester 23, which affords ketone 24 as the major stereomer, has also been studied as a model. Ozonolysis of 24 led to the known (S)-keto aldehyde 25 (unpublished results). (Equation Presented)
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37
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84958315401
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Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpi, F. J. Am. Chem. Soc. 1991, 113, 1047.
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Urpi, F.4
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38
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0000730312
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and references therein
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Evans, D. A.; Dart, M. J.; Duffy, J. L.; Rieger, D. L. J. Am. Chem. Soc. 1995, 117, 9073 and references therein.
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Rieger, D.L.4
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39
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0024346385
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Dirlam, J. P.; Belton, A. M.; Chang, S. P.; Cullen, W. P.; Huang, L. H.; Kojima, Y.; Maeda, H.; Nishiyama, S.; Oscarson, J. R.; Sakakibara, T. J. Antibiot. 1989, 42, 1213.
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Dirlam, J.P.1
Belton, A.M.2
Chang, S.P.3
Cullen, W.P.4
Huang, L.H.5
Kojima, Y.6
Maeda, H.7
Nishiyama, S.8
Oscarson, J.R.9
Sakakibara, T.10
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