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σ,π Interaction in Halogen-Substituted Biadamantylidene Radical Cations

Nelsen, Stephen F. and Klein, Susan J. and Trieber, Dwight A., II and Ismagilov, Rustem F. and Powell, Douglas R. (1997) σ,π Interaction in Halogen-Substituted Biadamantylidene Radical Cations. Journal of Organic Chemistry, 62 (19). pp. 6539-6546. ISSN 0022-3263. https://resolver.caltech.edu/CaltechAUTHORS:20130821-160727814

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Abstract

The order of E°‘ and vIP for 4-eq-halogenated-biadamantylidene is F > Cl Br, and the 5-F-substituted compound is harder to ozidize than the 4-eq-F-substituted one. The former result is most consistent with a detectable resonance contribution through the σ-framework, and the latter with σ-hyperconjugative destablilization proceeding through two pathways being more than double the same effect through one pathway (the Whiffen effect). AM1 calculations predict these results. The facial selectivity for epoxidation and diazetidine formation from 4-eq-halogenated 3 (4(X)) is in the order Cl > F > Br, and the 5-fluoro compound (8) is less selective than 4(F) for both reactions. Steric as well as electronic factors might well contribute to these results, neither of which was expected from consideration of σ,π interaction. Cation radical catalyzed chain dioxetane formation from 4(F) and 3(Cl) is significantly more face selective than epoxidation or diazetidine formation, as expected on electronic grounds; σ,π interaction should be larger in the radical cation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jo970252rDOIArticle
http://pubs.acs.org/doi/full/10.1021/jo970252rPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jo970252rPublisherSupporting Information
ORCID:
AuthorORCID
Ismagilov, Rustem F.0000-0002-3680-4399
Additional Information:Copyright © 1997 American Chemical Society. Published In Issue: September 19, 1997. Received February 11, 1997. We thank the National Science Foundation for partial financial support of this work under grants CHE-9105485 and 9417946, as well as the Department of Education for a fellowship for S.J.K. Supporting Information Available: ^1H NMR spectra of 4(F), 4(Br), 8, and 9β/9α mixture and ^(13)C NMR spectra of 8, 9α, and 9β (7 pages).
Funders:
Funding AgencyGrant Number
NSFCHE-9105485
NSFCHE-9417946
Department of EducationUNSPECIFIED
Subject Keywords:oxy-cope rearrangement; face selectivity; 5-substituted adamantanones; nucleophilic-addition; cyclic voltammetry; chemical-shifts; ab-initio; adamantylideneadamantane; oxygenation; reduction
Issue or Number:19
Record Number:CaltechAUTHORS:20130821-160727814
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130821-160727814
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:40847
Collection:CaltechAUTHORS
Deposited By: Whitney Barlow
Deposited On:29 Aug 2013 18:37
Last Modified:03 Oct 2019 05:43

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