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Volumn 125, Issue 26, 2003, Pages 7942-7947

Tandem polar/radical crossover sequences for the formation of fused and bridged bicyclic nitrogen heterocycles involving radical ionic chain reactions, and alkene radical cation intermediates, performed under reducing conditions: Scope and limitations

Author keywords

[No Author keywords available]

Indexed keywords

IONIC CHAIN REACTIONS;

EID: 0038540780     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja035639s     Document Type: Article
Times cited : (43)

References (62)
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    • A closely related scheme was also advanced earlier by Sprecher: Sprecher, M. Chemtracts: Org. Chem. 1994, 7, 115.
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    • For example, time-resolved LFP studies of alkene radical cations generated according to Scheme 3 using a nanosecond laser only detect the diffusively free radical cation and so are unable to provide data on the rates of formation of contact ion pairs or of their trapping. This situation arises because diffusion out of the contact ion pair is expected to be faster than the nanosecond time scale of the instrument: Arnold, B. R.; Noukakis, D.; Farid, S.; Goodman, J. L.; Gould, I. R. J. Am. Chem. Soc. 1995, 117, 4399. For a discussion, see ref 14c.
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    • note
    • -1 in acetonitrile (both at 20 °C).
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    • note
    • -1.
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    • note
    • 1H NMR spectrum, which facilitates interpretation of spectra of crude reaction mixtures.
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    • It should be noted that Zipse has considered substitutions closely related to the ones employed here as concerted displacements accelerated by the adjacent radical rather than as dissociative mechanisms. The balance of the experimental evidence, however, favors the dissociative pathway, and the computations continue to move in this direction with each successive cycle of refinement: Zipse, H. Acc. Chem. Res. 1999, 32, 571.
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    • Indeed, Scifinder Scholar locates >2000 substances containing the 1-azabicyclo[3.2.1]octane nucleus with the majority in the medicinal and patent literature, suggesting that this may be an example of a "privileged structure": (a) Ariens, E. J.; Beld, A. J.; Rodrigues de Miranda, J. F.; Simonis, A. M. In The Receptors: A Comprehensive Treatise; O'Brien, R. D., Ed.; Plenum: New York, 1979; Vol. 1, pp 33.
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    • note
    • It is interesting to note that, although tributyltin hydride is not soluble in acetonitrile, and indeed partitioning between acetonitrile and hexanes is a favorite method for the removal of organotin byproducts from more polar products, there is sufficient solubility in a hot 1/1 mixture of benzene and acetonitrile for chain reactions to proceed smoothly.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.