Linked Life Data

12816495

Source:http://linkedlifedata.com/resource/pubmed/id/12816495

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
13
pubmed:dateCreated
2003-6-20
pubmed:abstractText
The crystalline peroxide 3a is the main product (out of 10 theoretically possible) from the aerial peroxidation of all-cis-2,4,6-trimethyltetrahydropyran (2a). It has a similar structure both in solution and in the crystal as shown by nuclear Overhauser effects and X-ray analysis, respectively. Theoretical calculations at a density functional theory level (B3LYP/6-31G) provide insight into the stabilities of the different stereoisomers of this peroxide, accounting for the facile, acid-catalyzed isomerization from the meso form to the racemate. Peroxide 3b, which is the 2-tert-butyl analogue of 3a, out of 22 theoretically possible isomers, crystallizes in a similar meso form. As a result of crystal packing effects and the intrinsically (axial) chiral peroxy "chromophore" that deviates slightly from the antiperiplanar conformation, both enantiomorphic forms of 3b are encountered in the lattice.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Jun
pubmed:issn
0022-3263
pubmed:author
pubmed:issnType
Print
pubmed:day
27
pubmed:volume
68
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
5331-8
pubmed:year
2003
pubmed:articleTitle
meso-Tetrahydropyranylperoxides: molecular structures in solution, in the crystal, and by DFT calculations and their isomerization to the racemate.
pubmed:affiliation
Forschungszentrum Karlsruhe, Institute for Nanotechnology, Postfach 3640, D-76201 Karlsruhe, Germany. silviu.balaban@int.fzk.de
pubmed:publicationType
Journal Article