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85088723371
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3SiH (4 mmol) in DCE (5 mL) under an oxygen atmosphere for 4 h gave 10-[(triethylsilyl)oxy]decan-2-yl triethylsilyl peroxide (30) (21%) together with 2-[(triethylsilyl)dioxy]decanol (31) (61%). In the absence of the Co(II) catalyst, however, 9-decenol remained intact. (diagram presented).
-
-
-
-
38
-
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0032809580
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The key intermediate 10 is most likely to be produced by electron transfer from the hydroperoxide 7 to the adventitious Co(III) complexes, followed by deprotonation. Goldstein, S.; Meyerstein, D. Acc. Chem. Res. 1999, 32, 547.
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Ando, W., Ed.; Wiley: New York; Chapter 2
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Spontaneous rearrangement of allyl hydroperoxides via the corresponding peroxy radical is well-known: (a) Porter, N. A. In Organic Peroxides; Ando, W., Ed.; Wiley: New York, 1992; Chapter 2
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0141584243
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note
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Compound 20 is most likely to be produced from the corresponding hydroperoxide by an oxygen atom transfer to unidentified reductants. In this respect, hydroperoxides with an electron-withdrawing group at the α-position are well-known to oxidize a variety of compounds such as alkene and sulfide.
-
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42
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0141472631
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Yamamoto, H.; Miura, M.; Nojima, M.; Kusabayashi, S. J. Chem. Soc., Perkin Trans. 1 1986, 473 and references therein.
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Komaromi, I.43
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Wong, M.W.55
Andres, J.L.56
Gonzalez, C.57
Head-Gordon, M.58
Replogle, E.S.59
Pople, J.A.60
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46
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0141472634
-
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note
-
In the case of the peroxy radical 22 the activation enthalpy and entropy leading to the formation of the transition state having a chair-chair conformation were calculated as 14.3 kcal/mol and -7.3 cal/mol, respectively.
-
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47
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0004104868
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de Mayo, P., Ed.; Academic Press: New York; Chapter 4
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