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Volumn 63, Issue 24, 1998, Pages 8704-8718

Photosensitized oxygenation of twisted 1,3-dienes: Abnormally higher reactivity of vinyl hydrogen rather than allyl hydrogen toward singlet oxygen

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; HYDROGEN; SINGLET OXYGEN;

EID: 0031768803     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo980955o     Document Type: Article
Times cited : (28)

References (93)
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    • note
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    • It has been well-known that the molar absorptivity in electronic spectra shows the probability of the activation to the excited state of molecules. Therefore, it has been pointed that there is some relationship between the molar absorptivity and the torsion angle of two unsaturated bonds in 1,3-dienes. In the present cases, however, measurement of the exact molar absorptivity of 10b-d was unfortunately very difficult. On the other hand, maximum absorption values of 10a-d show whether the 1,3-dienes in these molecule are conjugated: Hedden, G. D.; Brown, W. G. J. Am. Chem. Soc. 1953, 75, 3744.
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    • Schuster and co-workers measured the activation parameters of the reaction of singlet oxygen with cis-alkenes and suggested that in the rate-determining step there is some type of "positive interaction" between the oxygen and two allylic hydrogens of cis-olefins: (a) Hurst, J. R.; McDonald, J. D.; Schuster, G. B. J. Am. Chem. Soc. 1982, 104, 206. (b) Hurst, J. R.; Wilson, S. L.; Schuster, G. B. Tetrahedron 1985, 41, 2191.
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    • Schuster and co-workers measured the activation parameters of the reaction of singlet oxygen with cis-alkenes and suggested that in the rate-determining step there is some type of "positive interaction" between the oxygen and two allylic hydrogens of cis-olefins: (a) Hurst, J. R.; McDonald, J. D.; Schuster, G. B. J. Am. Chem. Soc. 1982, 104, 206. (b) Hurst, J. R.; Wilson, S. L.; Schuster, G. B. Tetrahedron 1985, 41, 2191.
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