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c) A. Martinez-Grau, D. P. Curran, J. Org. Chem. 1995, 60, 8332; D. P. Curran, J. Xu, E. Lazzarini, J. Am. Chem. Soc. 1995, 117, 6603; A. Martinez-Grau, D. P. Curran, Tetrahedron 1997, 53, 5679;
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d) D. P. Curran, J. Xu, Synlett 1997, 1102. For other UMCTreactions see: G. E. Keck, E. J. Enholm, J. B. Yates, M. R. Wiley, Tetrahedron 1985, 41, 4079; S. Kim, J. S. Koh, J. Chem. Soc. Chem. Commun. 1992, 1377; J. Boivin, J. Camara, S. Z. Zard, J. Am. Chem. Soc. 1992, 114, 7909.
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d) D. P. Curran, J. Xu, Synlett 1997, 1102. For other UMCTreactions see: G. E. Keck, E. J. Enholm, J. B. Yates, M. R. Wiley, Tetrahedron 1985, 41, 4079; S. Kim, J. S. Koh, J. Chem. Soc. Chem. Commun. 1992, 1377; J. Boivin, J. Camara, S. Z. Zard, J. Am. Chem. Soc. 1992, 114, 7909.
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d) D. P. Curran, J. Xu, Synlett 1997, 1102. For other UMCTreactions see: G. E. Keck, E. J. Enholm, J. B. Yates, M. R. Wiley, Tetrahedron 1985, 41, 4079; S. Kim, J. S. Koh, J. Chem. Soc. Chem. Commun. 1992, 1377; J. Boivin, J. Camara, S. Z. Zard, J. Am. Chem. Soc. 1992, 114, 7909.
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d) D. P. Curran, J. Xu, Synlett 1997, 1102. For other UMCTreactions see: G. E. Keck, E. J. Enholm, J. B. Yates, M. R. Wiley, Tetrahedron 1985, 41, 4079; S. Kim, J. S. Koh, J. Chem. Soc. Chem. Commun. 1992, 1377; J. Boivin, J. Camara, S. Z. Zard, J. Am. Chem. Soc. 1992, 114, 7909.
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43
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0344426470
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note
-
3.
-
-
-
-
44
-
-
0344858276
-
-
note
-
3 with subsequent chlorodeamination according to ref. [20]. The stannylated chlorosilane was isolated in 60% purity.
-
-
-
-
45
-
-
0344426469
-
-
note
-
3SiH over three steps (see Experimental Section). The chlorosilane was not easily purified and was used in 60-80% purity for the subsequent silylation reaction.
-
-
-
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46
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33845558052
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For a compilation of Si-Si bond energies see: R. Walsh. Acc. Chem. Res. 1981, 14, 246.
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37049087661
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S. J. Cole, J. N. Kirwan, B. P. Roberts, C. R. Willis, J. Chem. Soc. Perkin Trans 1 1991, 103. See also: C. Chatgilialoglu, K. U. Ingold, J. C. Scaiano, J. Am. Chem. Soc. 1983, 105, 3292.
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Cole, S.J.1
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48
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0000211999
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S. J. Cole, J. N. Kirwan, B. P. Roberts, C. R. Willis, J. Chem. Soc. Perkin Trans 1 1991, 103. See also: C. Chatgilialoglu, K. U. Ingold, J. C. Scaiano, J. Am. Chem. Soc. 1983, 105, 3292.
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51
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0345721158
-
-
note
-
6 and analysed prior to the removal of the solvent.
-
-
-
-
52
-
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0032569916
-
-
For 9 and 11 small amounts of an arylated side product were observed; this was formed by a 1,5-phenyl transfer from silicon to carbon. With secondary radicals this aryl transfer is the main reaction: A. Studer, M. Bossart, H. Steen, Tetrahedron Lett. 1998, 39, 8829.
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53
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0345289581
-
-
note
-
Silyl ethers derived from primary alcohols cyclize much slower than their congeners derived from secondary or tertiary alcohols (see below). For the fast cyclizing systems it was difficult to isolate pure radical precursors, because traces of an initiator can start the UMCT reaction and thus lead to decomposition of the starting material.
-
-
-
-
56
-
-
0344858270
-
-
note
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3).
-
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57
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0001528625
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D. P. Curran, M.-H. Chen, D. Kim, J. Am. Chem. Soc. 1989, 111, 6265.
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D. P. Curran, A. A. Martin-Esker, S.-B. Ko, M. Newcomb, J. Org. Chem. 1993, 58, 4691.
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59
-
-
0344858269
-
-
note
-
All the compounds were prepared as racemic mixtures.
-
-
-
-
60
-
-
0345289579
-
-
note
-
The relative configuration was assigned after transformation of 33 to the corresponding known diol derivative by Tamao-Fleming oxidation, see below. 3-Phenyl-2-pentanol (35%, u:l = 10:1) was formed as the main product. This product derives from a stereoselective 1,5 phenyl transfer from Si to C with subsequent desilylation: A. Studer, M. Bossart, H. Steen, réf. [21].
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61
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0345289580
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note
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The sun lamp was placed very close to the reaction vessel (sealed tube, T> 100°C). The relative configuration was assigned in analogy.
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62
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0345289578
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note
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Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-102599 (trans-41). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam. ac.uk). The X-ray analysis was carried out by Dr. V. Gramlich (ETH Zürich).
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