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The general methodology for macrolactones synthesis can often be applied for medium ring lactones. For a recent review: Parenty, A.; Moreau, X.; Campagne, J. M. Chem. Rev. 2006, 106, 911.
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The general methodology for macrolactones synthesis can often be applied for medium ring lactones. For a recent review: Parenty, A.; Moreau, X.; Campagne, J. M. Chem. Rev. 2006, 106, 911.
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Part of this work was reported as a preliminary communication: Ferraz, H. M. C.; Longo, L. S., Jr. Org. Lett. 2003, 5, 1337.
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34247181354
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For experimental details and full characterization data of 1a, 1b, and 1d see ref 27. For a general procedure for the preparation of 1c, 1e, and 1f, see Supporting Information
-
For experimental details and full characterization data of 1a, 1b, and 1d see ref 27. For a general procedure for the preparation of 1c, 1e, and 1f, see Supporting Information.
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34
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35
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34247229868
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Performing the reaction with 4.0 equiv of NaH in anhydrous THF led to the exclusive formation of the allylic alcohol 5 along with recovered starting material after 3 h under reflux. It is noteworthy that 5 was the only regioisomer observed with either KOH or NaH.
-
Performing the reaction with 4.0 equiv of NaH in anhydrous THF led to the exclusive formation of the allylic alcohol 5 along with recovered starting material after 3 h under reflux. It is noteworthy that 5 was the only regioisomer observed with either KOH or NaH.
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36
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2542433188
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The use of acetonitrile, as established by Sharpless and co-workers, represents a great improvement in the reaction protocol, since this solvent can prevent coordination of low-valent ruthenium species with carboxylic acids formed as byproducts during the course of the reaction. Carlsen, H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org. Chem. 1981, 46, 3936.
-
The use of acetonitrile, as established by Sharpless and co-workers, represents a great improvement in the reaction protocol, since this solvent can prevent coordination of low-valent ruthenium species with carboxylic acids formed as byproducts during the course of the reaction. Carlsen, H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org. Chem. 1981, 46, 3936.
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37
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34247235840
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A saturated aqueous solution of sodium sulfite (Na2SO 3) is also used in the workup protocols of ruthenium tetraoxide-mediated oxidations see ref 22
-
3) is also used in the workup protocols of ruthenium tetraoxide-mediated oxidations (see ref 22).
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38
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34247188745
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For the 1H and 13C NMR spectra of the keto-lactones 7g-j see ref 26
-
13C NMR spectra of the keto-lactones 7g-j see ref 26.
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Diketone 10 exists predominantly in the enol form: Snider, B. B.; Shi, Z. J. Am. Chem. Soc. 1992, 114, 1790.
-
Diketone 10 exists predominantly in the enol form: Snider, B. B.; Shi, Z. J. Am. Chem. Soc. 1992, 114, 1790.
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-
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45
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34247254009
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For experimental details and full characterization data of products 11 and 12 see Supporting Information.
-
For experimental details and full characterization data of products 11 and 12 see Supporting Information.
-
-
-
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47
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34247239505
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An example of the RuO4-promoted oxidation of a formate ester to the corresponding ketone is described in ref 25
-
4-promoted oxidation of a formate ester to the corresponding ketone is described in ref 25.
-
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48
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34247280160
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2O were based on n = 1.
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2O were based on n = 1.
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