Oxidative intramolecular cyclization of diketoximes: Synthesis of 1,5-dinitro-cis-bicyclo[3.3.0]octane

Journal of Organic Chemistry

Volumn 61, Issue 10, 1996, Pages 3545-3547

  Zajac Jr , Walter W ^a   Speier, Gary J ^a   Buzby, John H ^a   Walters, Thomas R ^a  

^a VILLANOVA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BICYCLO[3.3.0]OCTANE DERIVATIVE; NITRO DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029894892     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo950596m     Document Type: Article

References (33)

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8. If the bond scission is the result of a Grob fragmentation, then it is likely to occur when one, or both, of the nitrogen atoms is oxidized to the hydroxylamino oxidation state wherein the hydroxyl function may serve as an effective leaving group. The "push-pull" mechanism is postulated to become operational when electron pair donation from a less oxidized nitrogen (e.g., amino or hydroxylamino) provides "the push" toward a more highly oxidized nitrogen, "the pull" (e.g., nitroso or nitro) which facilitates the bond scission process. Theoretical aspects of the latter mechanism are considered in the following: (a) Murray, J. S.; Concha, M.; Seminario, J. M.; Politzer, P. J. Phys. Chem. 1991, 95, 1601. (b) Murray, J. S.; Seminario, J. M.; Politzer, P. Struct. Chem. 1991, 2, 153.
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33. The author has deposited atomic coordinates for this structure with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.