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Volumn 29, Issue 11, 2010, Pages 2406-2412

Fragmentation of β-silyl radicals. A computational study

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; COMPUTATION THEORY; FREE RADICALS;

EID: 77953199277     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om900940n     Document Type: Article
Times cited : (4)

References (73)
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    • For recent reports concerning the reduction of the amount of tin residues in radical reactions, see: and references therein
    • For recent reports concerning the reduction of the amount of tin residues in radical reactions, see: Dumartin, G.; Pourcel, M.; Delmond, B.; Donard, O.; Pereyre, M. Tetrahedron Lett. 1998, 39, 4663, and references therein.
    • (1998) Tetrahedron Lett. , vol.39 , pp. 4663
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    • Yorimitsu, H.1    Oshima, K.2
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    • For some reports on the generation of silyl radicals, see
    • For some reports on the generation of silyl radicals, see: Sakurai, H.; Hosomi, A. J. Am. Chem. Soc. 1971, 93, 1709
    • (1971) J. Am. Chem. Soc. , vol.93 , pp. 1709
    • Sakurai, H.1    Hosomi, A.2
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    • Such an allylation is not possible using the corresponding allyltrimethylsilane, as the corresponding β-silyl radical does not fragment. For instance, no reaction was observed during reaction of thiyl radicals with allyltrimethylsilanes, indicating that while addition of thiyl radical on the olefin is a fast process, β-elimination of a S-centered radical is faster than that of a silyl radical
    • Such an allylation is not possible using the corresponding allyltrimethylsilane, as the corresponding β-silyl radical does not fragment. For instance, no reaction was observed during reaction of thiyl radicals with allyltrimethylsilanes, indicating that while addition of thiyl radical on the olefin is a fast process, β-elimination of a S-centered radical is faster than that of a silyl radical: Light, J. P., II; Ridenour, M.; Beard, L.; Hershberger, J. W. J. Organomet. Chem. 1987, 326, 17
    • (1987) J. Organomet. Chem. , vol.326 , pp. 17
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    • In comparison, kinetic and stereochemistry of β-fragmentation of analogous β-sulfur radical species have been examined more thoroughly; see
    • In comparison, kinetic and stereochemistry of β-fragmentation of analogous β-sulfur radical species have been examined more thoroughly; see: Wagner, P. J.; Sedon, J. H.; Lindstrom, M. J. J. Am. Chem. Soc. 1978, 100, 2579
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    • references therein
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