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c) A. Kittaka, N. Yamada, H. Tanaka, K. T. Nakamura, T. Miyasaka, Nucleosides Nucleotides 1996, 15, 1447-1457.
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Evidence that C-1′ radicals play an important role in radical induced DNA damage has been reported; for recent reviews, see: a) W. K. Pogozelski, T. D. Tullius, Chem. Rev. 1998, 98, 1089-1107;
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19
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C-1′ acylated derivatives of 2′-deoxyuridine have recently been synthesized and shown to generate efficiently C-1′ radicals upon irradiation with UV light: a) C. Chatgilialoglu, T. Gimisis, Chem. Commun. 1998, 1249-1250;
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c). M. Greenberg, D. J. Yoo, B. K. Goodman, Nucleosides Nucleotides 1997, 16, 33-40;
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Similar results have also been reported by others: a) A. Kittaka, H. Tanaka, H. Kato, Y. Nonaka, K. T. Nakamura, T. Miyasaka, Tetrahedron Lett. 1997, 36, 6421-6424;
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0346220692
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note
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An Ortep diagram of 8 is reported in our preliminary communication, see ref. [11b]. However, it is worth mentioning that the oxazolo[3,4-c]pyrimidine moiety is flat and that the dihedral angle between the five-membered ring and the fused pyrimidine moiety is close to orthogonal.
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0346851246
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Tanaka and co-workers [12a] have reported similar results for 6b (yield 43%, β:α = 35:1) and 13 (yield 68%, β:α = 1:1.7) by using HPLC analysis. The discrepancy in the anomeric composition in the 2′-deoxyribo derivative cannot be rationalized without their detailed experimental conditions.
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43
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0346220691
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note
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A large number of reactions involving a 1,5-hydrogen transfers from carbon to oxygen is known ref. [21]. For example, this process is the key step in the Barton nitrile ester photolysis ref. [22a-c].
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44
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0004032955
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(Ed.: J. K. Kochi), Wiley, New York, Ch. 8
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For earlier work, see: a) J. W. Wilt in Free Radicals, Vol. 1 (Ed.: J. K. Kochi), Wiley, New York, 1973, Ch. 8;
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Beckwith, A.L.J.1
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a) For the original work, see: D. H. R. Barton, J. M. Beaton, L. E. Geller, M. M. Pechet, J. Am. Chem. Soc. 1961, 83, 4076-4083;
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d) for earlier work on the use of Barton-type hydrogen migration with formation of spiro compounds, see: G. Descotes, Bull. Soc. Chim. Belg. 1982, 91, 973-983.
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Descotes, G.1
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85087246729
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3) only 50% conversion was observed after 5 h for reaction 13→11+14 in Scheme 4.
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For some related examples of 1,5-radical translocation, see: a) J. Griffiths, J. A. Murphy, Tetrahedron 1992, 48, 5543-5556;
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The 5-endo-trig free radical cyclizations are a rare class of reactions, which is in agreement with the Baldwin - Beckwith rules ref. [30] indicating the reactions as unfavorable, since only a few examples of pent-4-enyl radical type cyclizations [31] are known. However, many examples are reported in the last few years, mainly by the groups of Ikeda in ret. [32] and Parsons in ref. [33], which show that carbamoylmethyl radicals cyclize in 5-endo mode to give γ-lactones.
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b) H.-G. Schmalz, S. Siegel, J. W. Bats, Angew. Chem. 1995, 107, 2597-2599; Angew. Chem. Int. Ed. Engl. 1995, 34, 2383-2385;
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0348111849
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note
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The β-fragmentation method has been used as an effective alternative to the tin hydride method to promote relatively slow cyclizations [35]. β-Stannyl, thiyl, and sulfonyl radical fragmentations have recently been used in synthesis to propagate radical reactions, ref. [36]. The use of the β-bromo fragmentation methodology is a useful and simple alternative which has been explored only recently, see ref. [37].
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0346851265
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For example, see: C. Chatgilialoglu, P. Renaud, in General Aspects of Free Radical Chemistry (Ed.: Z. B. Alfassi), Wiley, London, 1999, pp. 501-538.
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J. M. Tanko, M. Sadeghipour, Angew. Chem. 1999, 111, 159-161; Angew. Chem. Int. Ed. 1999, 38, 159-161.
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Tanaka and co-workers [12b] have reported that an iodo derivative in the ribo series analogous to 31 gave the corresponding spironucleoside under reducing conditions with Bu3SnH.
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However, the C1′-N1 bond rotation and the relative populations of the rotamers may also play a role in the cyclization.
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For example, see: A. F. Markham, S. Uesugi, E. Ohtsuka, M. Ikehara, Biochemistry 1979, 18, 4936-4942; A. Galat, A. Jankowski, Biochemistry 1982, 21, 849-858; W. Guschlbauer, Y. Courtois, FEBS Lett. 1968, 1, 183-186.
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