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27644472079
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note
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Activation energies were calculated relative to isolated reactants.
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28
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27644555002
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note
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DMDO is included in the Supporting Information.
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37
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0000845829
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1 led to a decrease in energy by 2.3 kcal/mol. A lowering of energy by 1.9 kcal/mol was noted for methane oxidation by dioxirane: see ref 16. Also see: (a) Du, X.; Houk, K. N. J. Org. Chem. 1998, 63, 6480-6483.
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39
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27644546123
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note
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The reaction of oxaziridine 3 and 1-decene or adamantane affords the oxidized products with reaction times and product conversions comparable to that of 5. Difficulties associated with the chromatographic separation of the benzoxathiazine byproduct from the desired compounds in addition to the high cost of the starting 2-bromophenol caused us to favor the use of benzoxathiazine 4 for all subsequent experiments.
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40
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27644536507
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note
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1,3-Adamantanediol was produced in small quantities (∼5%) along with trace levels of 2-adamantanone. The absence of halogenated products suggests that freely diffusing radical species are not formed.
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41
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0035815164
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2 is very easily prepared in a single operation (80%). See: (a) ten Brink, G.-J.; Vis, J.-M.; Arends, I. W. C. E.; Sheldon, R. A. J. Org. Chem. 2001, 66, 2429-2433.
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0035819724
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(b) ten Brink, G.-J.; Fernandes, B. C. M.; van Vliet. M. C. A.; Arends, I. W. C. E.; Sheldon, R. A. J. Chem Soc., Perkin Trans. 1 2001, 224-228.
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43
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84889491424
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27644533113
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note
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2 and UHP gave <10% conversion to epoxide.
-
-
-
-
45
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27644537843
-
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note
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Attempts to oxidize benzylic substrates afforded mixtures of products presumably due to aromatic functionalization.
-
-
-
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46
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0000963419
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Trans-decalin affords ∼15% yield of trans-9-decalinol with no isomerization to the cis product detected by GC. DMDO oxidizes trans-decalin to trans-9-decalinol in 20% yield. See: Murray, R. W.; Jeyaraman, R.; Mohan, L. J. Am. Chem. Soc. 1986, 108, 2470-2472.
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27644542568
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note
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1H NMR. Under the same catalytic conditions, isoamyl benzoate showed 5% conversion to the hydroxylated product after 24 h. Collectively, these data suggest that the selectivity observed in the hydroxylation of dihydrocitronellol benzoate is principally determined by electronic effects.
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48
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0035962969
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