Linked Life Data

20957622

Source:http://linkedlifedata.com/resource/pubmed/id/20957622

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
47
pubmed:dateCreated
2010-12-14
pubmed:abstractText
We report herein a detailed investigation into the reaction mechanism for a sequential oxy-Cope/ene reaction under anionic conditions. With DFT calculations and ab initio molecular dynamics simulations, the observed diastereoselectivity is shown to be the result of an isomerization of the enolate olefin, which would evidently not occur under neutral conditions. The potential energy surface was thoroughly mapped out for the reaction pathways and the proposed mechanism confirmed the different product distributions observed under neutral and anionic oxy-Cope conditions. In addition, other possible pathways are shown to be higher in energy and experimental evidence is given that supports the olefin-isomerization pathway.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Dec
pubmed:issn
1521-3765
pubmed:author
pubmed:issnType
Electronic
pubmed:day
17
pubmed:volume
16
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
14124-30
pubmed:meshHeading
pubmed:year
2010
pubmed:articleTitle
On the origin of altered diastereomeric ratios for anionic versus neutral reaction conditions in the oxy-Cope/ene reaction: an interplay of experiment and computational modeling.
pubmed:affiliation
Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, K1N?6N5 ON, Canada.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't