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Volumn 122, Issue 30, 2000, Pages 7317-7326

Oxidative single-electron transfer activation of σ-bonds in aliphatic halogenation reactions

Author keywords

[No Author keywords available]

Indexed keywords

ADAMANTANE DERIVATIVE; ALKANE DERIVATIVE; HYDROCARBON;

EID: 0034596316     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000193q     Document Type: Article
Times cited : (56)

References (126)
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    • (1992) Advances in Strain in Organic Chemistry , vol.2 , pp. 1
    • Szeimies, G.1
  • 30
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    • Electrophilic Additions to Bicyclo[1.1.0]butanes
    • Halton, B., Ed.; JAI Press Ltd.: London
    • Christl, M. Electrophilic Additions to Bicyclo[1.1.0]butanes. In Advances in Strain in Organic Chemistry; Halton, B., Ed.; JAI Press Ltd.: London, 1995; Vol. 4, p 163.
    • (1995) Advances in Strain in Organic Chemistry , vol.4 , pp. 163
    • Christl, M.1
  • 45
    • 0001833654 scopus 로고
    • My Thirty Years in Hydrocarbon Cages: From Adamantane to Dodecahedrane
    • Olah, G. A., Ed.; Wiley: New York
    • Schleyer, P. v. R. My Thirty Years in Hydrocarbon Cages: From Adamantane to Dodecahedrane. In Cage Hydrocarbons; Olah, G. A., Ed.; Wiley: New York, 1990; p 1.
    • (1990) Cage Hydrocarbons , pp. 1
    • Schleyer, P.V.R.1
  • 55
    • 0343605479 scopus 로고    scopus 로고
    • note
    • Vertical IPs were computed for the neutral hydrocarbon geometries where one electron was removed (i.e., a Franck - Condon state). As a consequence, these structures are not stationary and only serve as models for fast and reversible electron transfer in aliphatic hydrocarbons. This is the reason these "structures" are put in brackets in Schemes 4 and 5.
  • 80
    • 0342735426 scopus 로고    scopus 로고
    • note
    • + cation, modeling the electrophilic reaction with polarized dihalogen compounds. The geometry of the hydrocarbon moiety in this TS and the reaction barriers are quite similar to that found by Bach and Su for the hydroperoxonium ion reaction with isobutane.
  • 86
    • 0343169909 scopus 로고    scopus 로고
    • note
    • 3v minimum with a long C-H bond and hydrogen loss occurs as a one-step process.
  • 94
    • 0343605443 scopus 로고    scopus 로고
    • note
    • Adamantane photooxidation with 1,2,4,5-tetracyanobenzene (TCB) in acetonitrile proceeds with intermediate formation of the adamantyl radical cation; further fragmentation to the I-adamantyl radical occurs via elimination of a proton. We studied the KIE of this reaction experimentally for competitive adamantane and 1,3,5,7-tetradeuterioadamantane photooxidation using Mella's conditions (ref 96). The observed inverse KIE (0.90 ± 0.05) shows that proton loss is not included into the rate-limiting step. A detailed study will be published elsewhere.
  • 97
    • 0343169905 scopus 로고    scopus 로고
    • note
    • + cannot be excluded. Generally, it is difficult to differentiate between two possible ways of proton loss form hydrocarbon radical cations in the presence of a nucleophile, i.e., between direct proton transfer to the nucleophile and nucleophilic addition-elimination reactions.
  • 101
    • 0342735423 scopus 로고    scopus 로고
    • note
    • 2 is 6.9; for the chlorination with IC1 this value is 3.5.
  • 105
    • 0032479750 scopus 로고    scopus 로고
    • Schreiner, P. R.; Lauenstein, O.; Kolomitsyn, I. V.; Nadi, S.; Fokin, A. A. Angew. Chem. 1998, 110, 1993; Angew. Chem., Int. Ed. 1998, 37, 1895..
    • (1998) Angew. Chem., Int. Ed. , vol.37 , pp. 1895


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.