Linked Life Data

18558767

Source:http://linkedlifedata.com/resource/pubmed/id/18558767

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
14
pubmed:dateCreated
2008-7-11
pubmed:abstractText
The generation of the title cation 2(+) and its reaction under solvolytic and non-nucleophilic conditions were investigated. When the precursor chlorocyclopentadiene 5 was reacted with silica gel that contained water or with anhydrous MeOH, the corresponding 5-hydroxy- and 5-methoxycyclopentadienes (7 and 6) were produced in 68 and 81% yields, respectively. This indicates that 2(+) is formed as an intermediate under solvolytic conditions and persists without any rearrangement of the homoadamantane frameworks, at least during the period before capture by the nucleophile. On the other hand, the abstraction of a chloride ion from 5 by Ag(+) in the absence of a nucleophile at -78 degrees C resulted in the quantitative formation of allyl cation 8(+), incorporated in a bicyclo[3.1.0]hexane framework, via the Wagner-Meerwein rearrangement of a homoadamantane framework. Cation 8(+) was isolated as the SbF6(-) salt, and its structure was determined by X-ray crystallography. Quenching this cation with MeOH afforded a methyl ether 14, with a cyclopentadiene structure retained but one of the homoadamantane frameworks had undergone a structural change by a further Wagner-Meerwein rearrangement.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Jul
pubmed:issn
1520-6904
pubmed:author
pubmed:issnType
Electronic
pubmed:day
18
pubmed:volume
73
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
5248-54
pubmed:year
2008
pubmed:articleTitle
Generation and reaction of a phenyl-substituted cyclopentadienyl cation annelated with two homoadamantene frameworks.
pubmed:affiliation
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
pubmed:publicationType
Journal Article