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Dimerization of α-hydroxy ketones: (a) Creary, X.; Rollin, A J. J. Org. Chem. 1977, 42, 4226.
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33750011223
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Isolation of methyl l-hydroxy-6-oxo-2-cyclohexenecarboxylate: (a) Rasmussen, B.; Nkurunziza, A.-J.; Witt, M.; Oketch-Rabah, H. A.; Jaroszewski, J. W.; Sterk, D. J. Nat. Prod 2006, 69, 1300.
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Isolation of methyl l-hydroxy-6-oxo-2-cyclohexenecarboxylate: (a) Rasmussen, B.; Nkurunziza, A.-J.; Witt, M.; Oketch-Rabah, H. A.; Jaroszewski, J. W.; Sterk, D. J. Nat. Prod 2006, 69, 1300.
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Richardson, A.M.1
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65249189478
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AZADO : (a) Tomizawa, M.; Shibuya, M.; Iwabuchi, Y. Org. Lett. 2009, 11, 1829.
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AZADO : (a) Tomizawa, M.; Shibuya, M.; Iwabuchi, Y. Org. Lett. 2009, 11, 1829.
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17
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33745700261
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19
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0000810296
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(a) Luca, L. D.; Giacomelli, G.; Porcheddu, A. Org. Lett. 2001, 3, 3041.
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20
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0037940081
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(b) Luca, L. D.; Giacomelli, G.; Másala, S.; Porcheddu, A. J. Org. Chem. 2003, 68, 4999.
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Luca, L.D.1
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21
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77749239293
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99.5% ee of (+)-7 was obtained in 44% yield after 24 h reaction under the same conditions, together with 77% ee of (+)-ketone 8 in. 54% yield. Oxidation of the highly enantiomerically enriched (+)-7 gave (-)-8 which was converted to unnatural idesolied (+)-1 (see the Supporting Information).
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99.5% ee of (+)-7 was obtained in 44% yield after 24 h reaction under the same conditions, together with 77% ee of (+)-ketone 8 in. 54% yield. Oxidation of the highly enantiomerically enriched (+)-7 gave (-)-8 which was converted to unnatural idesolied (+)-1 (see the Supporting Information).
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22
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21344465658
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Vedejs, E.; Jure, M. Angew. Chem., Int. Ed. 2005, 44, 3974.
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Vedejs, E.1
Jure, M.2
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23
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1842839850
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Kaburagi, Y.; Osajima, H.; Shimada, K.; Tokuyama, H.; Fukuyama, T. Tetrahedron Lett. 2004, 45, 3817.
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Kaburagi, Y.1
Osajima, H.2
Shimada, K.3
Tokuyama, H.4
Fukuyama, T.5
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26
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77749282236
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This diastereomer dissociated to the monomer 2 during silica gel column chromatography. Although we could not isolate the diastereomer, we obtained a mixture of the diastereomer and idesolide after gel filtration chromatography. The 13C NMR spectrum (see the Supporting Information) indicated that this diastereomer is the epimer at the ketal carbon
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13C NMR spectrum (see the Supporting Information) indicated that this diastereomer is the epimer at the ketal carbon.
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27
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77749257532
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AZADO-catalyzed dimerization of racemic monomer 2 gave racemic idesolide (rac-1) along with the diastereomer (diastereomer- Rac) consisting of (R)-2 and (S)-2. The structure of this diastereomer was confirmed by X-ray crystallography (see the Supporting Information). (Chemical Equetion Presentation)
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AZADO-catalyzed dimerization of racemic monomer 2 gave racemic idesolide (rac-1) along with the diastereomer (diastereomer- Rac) consisting of (R)-2 and (S)-2. The structure of this diastereomer was confirmed by X-ray crystallography (see the Supporting Information). (Chemical Equetion Presentation)
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19 brought about 45% ee (see the Supporting Information).
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19 brought about 45% ee (see the Supporting Information).
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29
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4143062549
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In light of the experimental results that the dimerization was promoted either by tertiary alkylamines or tertiary amine N-oxide, we speculate AZADO behaved as a possible general base, Chemical Equetion Presentation For hydrogen-bonding interactions between stable nitroxyl radical and ROH, see: (a) Morishima, I, Ishihara, K, Tomishima, K, Inubushi, T, Yonezawa, T. J. Am. Chem. Soc. 1975, 97, 2749
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In light of the experimental results that the dimerization was promoted either by tertiary alkylamines or tertiary amine N-oxide, we speculate AZADO behaved as a possible general base. (Chemical Equetion Presentation) For hydrogen-bonding interactions between stable nitroxyl radical and ROH, see: (a) Morishima, I.; Ishihara, K.; Tomishima, K.; Inubushi, T.; Yonezawa, T. J. Am. Chem. Soc. 1975, 97, 2749.
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(b) Otsuka, T.; Motozaki, W.; Nishikawa, K.; Endo, K. J. Mol. Struct. 2002, 615, 147.
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Otsuka, T.1
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(c) Russ, J. L.; Gu, J.; Tsai, K.-H.; Glass, T.; Duchamp, J. C.; Dorn, H. C. J. Am. Chem. Soc. 2007, 129, 7018.
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(a) Kinoshita, S.; Ohsaka, T.; Tokuda, K. Electrochem. Acta 2003, 48, 1589.
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Kinoshita, S.1
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Tokuda, K.3
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