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Volumn , Issue 9, 2005, Pages 1437-1444

Alkoxyl radicals as O-synthons in self-terminating radical oxygenations: An experimental and theoretical study

Author keywords

Alkynes; Computational chemistry; Oxidations; Photochemistry; Radicals

Indexed keywords

ACTIVATION ANALYSIS; ADDITION REACTIONS; HYDROCARBONS; KETONES; OXIDATION; RESONANCE;

EID: 20644445864     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2005-865330     Document Type: Article
Times cited : (12)

References (29)
  • 4
    • 20644448549 scopus 로고    scopus 로고
    • note
    • To our knowledge, rate data for the addition of alkoxyl radicals to alkynes have not been determined so far.
  • 14
    • 20644449428 scopus 로고    scopus 로고
    • PhD Thesis; Universität Kiel: Germany
    • . induced self-terminating radical oxygenations was verified by DFT calculations: Dreessen, T. PhD Thesis; Universität Kiel: Germany, 2004.
    • (2004)
    • Dreessen, T.1
  • 15
    • 0001053575 scopus 로고
    • Examples for the intermolecular addition of O-centered radicals to C=C triple bonds: (a) Walling, C.; Clark, R. T. J. Am. Chem. Soc. 1974, 96, 4530.
    • (1974) J. Am. Chem. Soc. , vol.96 , pp. 4530
    • Walling, C.1    Clark, R.T.2
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    • note
    • 4-8
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    • note
    • 8
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    • note
    • 4a
  • 23
    • 0036399236 scopus 로고    scopus 로고
    • Actually, the energy barrier for the addition of alkyl radicals to the carbonyl oxygen was calculated to be significantly higher than for the addition to the carbon site of a carbonyl bond: (a) Hippler, H.; Viskolcz, B. Phys. Chem. Chem. Phys. 2002, 4, 4663.
    • (2002) Phys. Chem. Chem. Phys. , vol.4 , pp. 4663
    • Hippler, H.1    Viskolcz, B.2
  • 26
    • 20644444282 scopus 로고    scopus 로고
    • note
    • Steric repulsion by the bulky methyl substituents may be the reason for the slightly longer O-X bond in the terf-butyl substituted radical 12.
  • 27
    • 20644432384 scopus 로고    scopus 로고
    • note
    • 16a
  • 28
    • 1842737688 scopus 로고    scopus 로고
    • This is in agreement with literature, where comparison of the reaction barriers for radical reactions with these two functionals has shown the B3LYP barriers to be somewhat too low, whereas the BHandHLYP barriers are slightly too high in many cases; see for example: Wang, Y.; Grimme, S.; Zipse, H. J. Phys. Chem. A 2004, 108, 2324.
    • (2004) J. Phys. Chem. A , vol.108 , pp. 2324
    • Wang, Y.1    Grimme, S.2    Zipse, H.3
  • 29
    • 20644443865 scopus 로고    scopus 로고
    • note
    • BHandHLYP calculations performed with the cc-pVDZ, aug-cc-pVDZ and cc-pVTZ basis set, respectively, resulted in comparable results for ΔE‡ and ΔE than obtained with the 6-311G** basis set. MP2 calculations with these basis sets generally reflected the results of the B 3LYP method.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.