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The Xenia diterpenoids of the xeniaphyllan class are based on the same core structure as the plant derived caryophyllans. For the recent first enantioselective synthesis of β-caryophellene see reference [6b]
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The Xenia diterpenoids of the xeniaphyllan class are based on the same core structure as the plant derived caryophyllans. For the recent first enantioselective synthesis of β-caryophellene see reference [6b]
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The RCM-based construction of monocyclic oxanonene systems has been reported, including structures with trisubstituted Z double bonds. See: a) M. T. Crimmins, J. M. Ellis, J. Org. Chem. 2007, 72, 1649-1660;
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57749119445
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In control experiments the two separated anomers of ketone 15 were treated with MeMgBr individually. For each anomer only one diastereoisomeric product was obtained in the addition reaction; however, the relative and absolute configuration of these products at C3 and C11 was not determined.
-
In control experiments the two separated anomers of ketone 15 were treated with MeMgBr individually. For each anomer only one diastereoisomeric product was obtained in the addition reaction; however, the relative and absolute configuration of these products at C3 and C11 was not determined.
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33
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57749118856
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Aldehyde 19 was obtained from the known propargylic alcohol 22 (THP = tetrahydropyranyl; D. Díez Martín, I. S. Marcos, P. Basabe, R. E. Romero, R. F. Moro, W. Lumeras, L. Rodríguez, J. Urones, Synthesis 2001, 1013-1022) in a four step sequence comprising PMB-protection of the tertiary hydroxyl group, removal of the THP group with p-toluene sulfonic acid, REDAL reduction to the E alkene and TPAP oxidation in 55% overall yield. Details of the synthesis will be published elsewhere.
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Aldehyde 19 was obtained from the known propargylic alcohol 22 (THP = tetrahydropyranyl; D. Díez Martín, I. S. Marcos, P. Basabe, R. E. Romero, R. F. Moro, W. Lumeras, L. Rodríguez, J. Urones, Synthesis 2001, 1013-1022) in a four step sequence comprising PMB-protection of the tertiary hydroxyl group, removal of the THP group with p-toluene sulfonic acid, REDAL reduction to the E alkene and TPAP oxidation in 55% overall yield. Details of the synthesis will be published elsewhere.
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34
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57749121958
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[6b]
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[6b]
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b) H. Sai, T. Ogiku, H. Ohmizu, Tetrahedron 2007, 63, 10345-10353.
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37
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57749099134
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The 1H NMR spectrum of synthetic blumiolide C corresponds exactly with the published data.[9] For the 13C NMR spectrum of synthetic 1 17 out of 20 signals match with the literature data within 0.1 ppm. Two carbonyl signals deviate by 0.6 ppm, which could simply be a consequence of different measuring conditions, See the Supporting Information, For the signal at 130.3 ppm in our spectrum the corresponding literature signal is reported at 133.0 ppm. We assume this to be a publication error in reference [9, 1: HRMS: calc. for [M+Na, 353.1723, found 353.1728; lit. HRFABMS calc. for [M, 331.1902, found 331.1905, α]D25, 50.0° (c, 0.4 g cm-3, CHCl3, lit, α]D25, 66.0° c, 0.4 g cm-3, CHCl3
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3).
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