Studies of 9-fluorenyl carbocations. Intramolecular hydride migration in a substituted 9-fluorenyl carbocation

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DOIResolve DOI: http://doi.org/10.1021/jo0009200
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TypeArticle
Journal titleThe Journal Of Organic Chemistry
ISSN0022-3263
Volume66
Issue4
Pages11091114; # of pages: 6
AbstractThe substituted fluorenyl cation, 9-(diphenylmethyl)fluoren-9-yl cation (4), is formed under stable ion conditions (low temperature/strong acid) from its corresponding alcohol 3. This ion is transformed to a substituted diphenyl methyl cation 8 at ambient temperature via an apparent 1,2-hydrogen shift. Irradiation of 9-(diphenylmethyl)fluoren-9-ol in methanol gives products derived from the corresponding cation along with radical-derived products from C-C and C-O homolysis processes. The laser flash photolysis of this alcohol gave a transient corresponding to cation 4. All of the photoproducts are derived from cation 4 or radical pathways. High level MO calculations point to a high barrier (23.8 kcal mol-1) for the 1,2-hydride shift. This barrier is the consequence of the minimum energy conformation of this fluorenyl cation which is less than ideal for the periplanar geometry necessary for this process.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedNo
Identifier10008226
NPARC number12328577
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Record identifierb5538f3c-b759-4e35-9ac0-ea315c32247e
Record created2009-09-10
Record modified2016-05-09
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