| The bicyclo[2.2.2]octyl carbene system as a probe for migratory aptitudes of hydrogen to carbenic centers. | |
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MedLine Citation:
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PMID: 11456755 Owner: NLM Status: PubMed-not-MEDLINE |
Abstract/OtherAbstract:
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A series of tosylhydrazone derivatives of exo-6-substituted bicylo[2.2.2]octan-2-ones have been prepared. Thermal decomposition of the sodium salts of these tosylhydrazones gives carbene-derived products from 1,3-migration of either the C6 hydrogen (perturbed) or the C7 hydrogen (unperturbed), along with smaller amounts of alkenes derived from 1,2-hydrogen migration. The exo-6-substituent strongly activates 1,3-hydrogen migration in the case of SiMe(3) and weakly activates it in the case of CH(3) substitution. Thiomethoxy and carbomethoxy are weakly deactivating, while cyano and methoxy groups are strongly deactivating. B3LYP/6-31G* calculations on these substituted carbenes and transition states are in qualitative agreement with the ease of 1,3-hydrogen migration of perturbed vs unperturbed hydrogen. These experimental results and computational studies suggest carbene stabilization due to the exo-6-silyl group. They also suggest a reactant-like transition state for 1,3-hydrogen migration in which the inductive effect influences ease of migration. In the case of the exo-6-methoxy group, the inductive effect overwhelms any potential resonance-stabilizing effects. |
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Authors:
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X Creary; M A Butchko |
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Publication Detail:
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Type: Journal Article |
Journal Detail:
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Title: Journal of the American Chemical Society Volume: 123 ISSN: 0002-7863 ISO Abbreviation: J. Am. Chem. Soc. Publication Date: 2001 Feb |
Date Detail:
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Created Date: 2001-07-17 Completed Date: 2001-10-11 Revised Date: 2003-10-31 |
Medline Journal Info:
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Nlm Unique ID: 7503056 Medline TA: J Am Chem Soc Country: United States |
Other Details:
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Languages: eng Pagination: 1569-78 Citation Subset: - |
Affiliation:
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Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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