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For a review on the synthesis of costunolide, 11β,13- dihydrocostunolide, and other germacrane sesquiterpenoids, see: A. J. Minnaard, B. P. A. W. Joannes, A. de Groot, Tetrahedron 1999, 55, 2115-2146.
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11844281849
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note
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1(10). Carbon-atom numbering corresponds to the germacrane system.
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34
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a) K. Bergstad, S. Jonson, J. E. Bäckvall, J. Am. Chem. Soc. 1999, 121, 10424-10425;
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11844281848
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note
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All of the products obtained, except 7 and 9, were isolated by flash chromatography and characterized by spectroscopic techniques including high resolution mass spectrometry and NMR spectroscopy.
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37
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11844251746
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note
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13C NMR spectra matched those reported for the natural product.[2a]
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38
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11844289927
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note
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The absolute stereochemistry of (+)-11β,13-dihydrocostunolide (5) was established by chemical correlation with (+)-costunolide (4).[10b]
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39
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For a rare example of ring contraction reactions from ten- to nine-membered carbocycles, see: X. Lei, C. Doubleday, Jr., N. J. Turro, Tetrahedron Lett. 1986, 27, 4675-4678.
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11844286610
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note
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For experimental details, see Supporting Information. [21] The interatomic distance between H-6 and H-15 of 10 is 3.789 Å in the minimized energy conformation shown in Figure 1 (CS Chem3D Pro, MOPAC).
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44
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