Linked Life Data

18303911

Source:http://linkedlifedata.com/resource/pubmed/id/18303911

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
6
pubmed:dateCreated
2008-3-17
pubmed:abstractText
The thermal Diels-Alder reaction between alkenylmetal(0) Fischer carbenes and 1,3-dienes (isoprene and cyclopentadiene) has been studied computationally within the density functional theory framework. The selectivity of the [4 + 2] cycloadditions between alkenyl-group 6 (Fischer) carbene complexes and isoprene is similar to the selectivity computed for the reactions involving Lewis acid complexed acrylates. The experimentally observed complete endo selectivity in the [4 + 2] cycloadditions of alkenyl-group 6 (Fischer) carbene complexes with cyclopentadiene, which takes place under kinetic control, may be due in part to the presence of stabilizing secondary orbital interactions. These interactions are stronger than the analogues in the metal-free processes. The [4 + 2] cycloadditions between alkenyl-group 6 (Fischer) carbene complexes and neutral dienes occur concertedly via transition structures which are more asynchronous and less aromatic than their non-organometallic analogues, a behavior which is extensible to the reactions between Lewis acid complexed acrylates.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Mar
pubmed:issn
0022-3263
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:volume
73
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2083-9
pubmed:year
2008
pubmed:articleTitle
DFT study on the Diels-Alder cycloaddition between alkenyl-M(0) (M = Cr, W) carbene complexes and neutral 1,3-dienes.
pubmed:affiliation
Departamento de Química OrgAnica, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain. israel@quim.ucm.es
pubmed:publicationType
Journal Article