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For a concise review, see: a) T. Wirth, Angew. Chem. 2001, 113, 2843; Angew. Chem. Int. Ed. 2001, 40, 2812.
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For an initial communication, see: J. Barluenga, F. González- Bobes, S. R. Ananthoju, M. A. García-Martín, J. M. González, Angew. Chem. 2001, 113, 3491; Angew. Chem. Int. Ed. 2001, 40, 3389.
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For a recent review focused on β-scission reactions, see: E. Suárez, M. S. Rodríguez in Radicals in Organic Chemistry. (Eds.: P. Renaud, M. P. Sibi), Wiley-VCH, Weinheim, 2001, pp. 440-454.
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38
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4644324373
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note
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All compounds give NMR and analytical data in accordance with the proposed structures.
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39
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4644301980
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note
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3 has been discussed previously and seems to be related to the deprotonation reaction of one of the plausible intermediates. This deprotonation would he crucial when the β-scission process was not a particularly favoured reaction. See reference [12].
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40
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0000814530
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(Eds.: B. M. Trost, I. Fleming, S. V. Ley), Pergamon Press, Oxford
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The cleavage of vicinal diols to produce α,ω-dialdehydes is a widely employed transformation. For a general overview, see: T. K. M. Shing in Comprehensive Organic Synthesis, Vol. 7 (Eds.: B. M. Trost, I. Fleming, S. V. Ley), Pergamon Press, Oxford, 1991, pp. 703-717.
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4644295913
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note
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3 and MgO were also tested, affording worse results in all cases.
-
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-
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44
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-
4644226373
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-
note
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In the absence of molecular sieves (MS 4 Å), small amounts (5-10%) of the corresponding acids were detected in the crude reaction mixtures.
-
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45
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-
4644350820
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-
note
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In the absence of tBuOH the desired esters were obtained in lower yields.
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46
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4644237919
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Esters are commonly observed as by-products in the oxidation of primary alcohols, although their selective preparation in this kind of homo-coupling process has rarely been reported and is normally restricted to intramolecular reactions. For leading references see: H. Tohma, T. Maegawa, Y. Kita, Synlett 2003, 723;
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+ species is responsible for reaction with the alkene; for leading work see: a) A. A. Neverov, H. X. Feng, K. Hamilton, R. S. Brown, J. Org. Chem. 2003, 68, 3802, and references therein. The differences between alcohols and alkenes as nucleophiles and, importantly, the participation of the inorganic base and its likely role of irreversibly removing a proton are among the reasons that may play a key role favouring the alternative path postulated here.
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The formation of these types of intermediates through the interaction of iodine-containing reagents and hydroxy groups is widely accepted. For spectroscopic evidence, sec: a) J. Madsen, C. Viuf, M. Bols, Chem. Eur. J. 2000, 6, 1140;
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3-iodanes related to E has been already pustulated: D. D. Tanner, G. C. Gidley, N. Das, J. E. Rowe, A. Potter, J. Am. Chem. Soc. 1984, 106, 5261. On the basis of these studies, the presence of different dimeric compounds cannot be discounted. For the sake of simplicity these plausible intermediates are not shown.
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For a general overview, see: M. Ochiai in Hypervalent Iodine Chemistry: Modern Developments in Organic Synthesis, (Ed.: T. Wirth), Springer, Berlin, 2003, pp. 5-68.
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4644252178
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This explains why only sub-stoichiometric amounts of this element were required to execute some of these transformations.
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59
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33845185356
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See also refs.[7a] and [21a]
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