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0010262764
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note
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15
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0029952618
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0026620712
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15. This is in contrast with the generally accepted idea that, at least in the field of nucleosides, they are normally formed from a cyclic oxocarbenium ion generated via exocyclic silylation of glycosides. For an exception, see: Jørgensen, T.; Pedersen, E. B.; Nielsen, C. Synthesis, 1992, 1299-1306.
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0000535305
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16. Gauche rotamers in a chain segment A-B-C-D are preferred electronically to their anti counterparts when A and D either are very electronegative relative to B and C or are unshared electron pairs. For some examples of this, see: (a) Labelle, M.; Morton, H. E.; Guindon, Y.; Springer, J. P. J. Am. Chem. Soc., 1988, 110, 4533-4540;
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22
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0010228527
-
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note
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4, the ether oxygen atom and the endocyclic acetal oxygen, probably due to the steric hindrance caused by the isopropoxy group.
-
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23
-
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0010228190
-
-
note
-
19. When the reaction was carried out on the cis/trans mixture of 5-isopropoxy-3-chloromethyl)-1,4-dioxepane even for 24 h, the starting material was recovered unchanged.
-
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24
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0027292263
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20. a) Nishigaichi, Y.; Takuwa, A.; Naruta, Y.; Maruyama, K. Tetrahedron, 1993, 49, 7395-7426;
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26
-
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0010287025
-
-
note
-
21. It is not plausible to accept the stabilization of the proximal incipient carbenium ion, which results from the leaving of the methoxy group to form a five-membered ring by the neighbouring-group participation of the chlorine or iodo atoms of 5g and 5h, for the following two reasons: a) trans-5g and trans-5h should be the major compounds but experimentally the cis products predominate, and
-
-
-
-
27
-
-
0029585983
-
-
b) neighbouring-group participation is well documented in carbohydrate chemistry, and is usually Lewis-acid independent; for this, see: Wilson, L. J.; Hager, M. W.; El-Kattan, Y. A.; Liotta, D. C. Synthesis, 1995, 1465-1479. (equation presented)
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0010262671
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note
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22. We now know the experimental conditions needed to direct the 5-FU nucleophilic-mediated tin (IV) chloride attack to the seven-membered methyl O,O-acetals 5 towards either the cyclic O,N-acetals type 3 or the acyclic ones type 4 (see ref. 12).
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29
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0001291157
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