Source:http://linkedlifedata.com/resource/pubmed/id/17450555
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
13
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| pubmed:dateCreated |
2007-7-19
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| pubmed:abstractText |
The sequential rearrangement reaction mechanism of the 2-allyl-2,4,5-hexatrienaldehyde has been studied at the unrestricted Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional (UB3LYP)/6-31G**, Complete Active Space Self-Consistent Field (CAS (8,8))/6-31G**, Configuration Interaction with Single and Double Excitations (CISD)//UB3LYP/6-31G** and the second-order perturbation theory based on the CASSCF reference wave function (CASPT2)//CAS(8,8)/6-31G** levels. Two pathways have been found to be involved for this reaction. The first pathway includes four processes of the rotation of the C3--C4 single bond, the stepwise [2 + 2] cycloaddition, the [1,5]-hydrogen migration, and the ring opening isomerization, while the second pathway undergoes only two processes of the [1,5]-hydrogen migration and the 8pi-electrocyclization. The calculation results indicate that the second pathway is favorable, in good agreement with the recent experimental observation. The whole reaction is stepwise and strong exothermic.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Oct
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| pubmed:issn |
0192-8651
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| pubmed:author | |
| pubmed:copyrightInfo |
(c) 2007 Wiley Periodicals, Inc.
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| pubmed:issnType |
Print
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| pubmed:volume |
28
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
2164-9
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| pubmed:year |
2007
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| pubmed:articleTitle |
A computational investigation on the sequential rearrangement mechanism of 2-allyl-2,4,5-hexatrienaldehyde involving [1,5]-hydrogen migration and 8pi-electrocyclization.
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| pubmed:affiliation |
Department of Chemistry, Sichuan University, Chengdu 610064, China.
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| pubmed:publicationType |
Journal Article
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