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Volumn 64, Issue 7, 1999, Pages 2250-2258

Oxetanes from [2+2] cycloaddition of stilbenes to quinone via photoinduced electron transfer

Author keywords

[No Author keywords available]

Indexed keywords

1,4 BENZOQUINONE; STILBENE DERIVATIVE;

EID: 0033515476     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981754n     Document Type: Article
Times cited : (42)

References (96)
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    • For a review that emphasizes the mechanistic considerations, see ref 2f
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    • Charge-transfer excitation of EDA complexes effects the transfer of an electron from the donor to the acceptor in less than 500 fs. See: Wynne, K.; Galli, C.; Hochstrasser, R. M. J. Chem. Phys. 1994, 100, 4797.
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    • See ref 15, p 40
    • See ref 15, p 40.
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    • The CT absorption band of the stilbene/chloranil EDA complex is centered at 510 nm. See ref 18
    • The CT absorption band of the stilbene/chloranil EDA complex is centered at 510 nm. See ref 18.
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    • note
    • • → oxetane
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    • note
    • (b) For the observation of 1,4-biradicals from the related benzoquinone and styrene, see:
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    • note
    • 27 (direct observation notwithstanding). Accordingly, we focus here on stilbene donors more closely akin to the original Paterno-Büchi substrates from which we could actually isolate the [2+2] cycloadducts and verify their oxetane structures by X-ray crystallography.
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    • Oxetenes are short-lived and exhibit lifetimes of up to several hours only at low temperatures. See: (a) Friedrich, L. E.; Bower, J. D. J. Am. Chem. Soc. 1973, 95, 6869.
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    • note
    • 30d
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    • Unpublished results (reported in ref 30b)
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    • note
    • The regiochemistry of the coupling could not be established by GC/MS analysis owing to complete decomposition of the spirooxetanes (to the starting materials) upon their injection into the gas chromatograph.
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    • With increasing oxidation potentials of the stilbene, the back electron transfer from stilbene cation radical to chloranil anion radical becomes more exergonic, and thus its rate constant will decrease in the Marcus-inverted region. See: (a) Marcus, R. A. Annu, Rev. Phys. Zhem. 1964, 15, 155.
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    • note
    • CT n Table 1.
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    • note
    • On the early picosecond time scale, the singlet ion-radical pair is observed due to CT excitation of the chloranil/stilbene EDA complex, which also absorbed at 406 nm (vide supra).
  • 89
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    • note
    • A detailed study of the solvent effects on the back electron transfer, the ion dissociation, and the coupling processes will be published later.
  • 90
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    • note
    • 23 is deternined by the relative orientation of the ion-radical pair, particularly is it is affected by the charge distribution. [As such, the spin nultiplicity of the singlet or triplet biradical state does not appear to be a distinguishing factor.] Charge annihilation in the triplet ion-radical pair may proceed either directly to the 1,4-biradical or via spin inversion followed by ion-pair collapse to the singlet 1,4-biradical.
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    • note
    • 47
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    • note
    • On deposit with the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB12 1EZ, U.K.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.