Source:http://linkedlifedata.com/resource/pubmed/id/11681954
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| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
22
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| pubmed:dateCreated |
2001-10-29
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| pubmed:abstractText |
The barriers to enantiomerization of a series of axially chiral biaryl analogues of 4-(dimethylamino)pyridine (DMAP) 1-10 were determined experimentally by means of dynamic HPLC measurements and racemization studies. The barriers to rotation in derivatives 1-6 (based on the bicyclic 5-azaindoline core) were lower than those in the corresponding derivatives 7-10 (based on the monocyclic DMAP core). Semiempirical (PM3), ab initio Hartree-Fock (HF/STO-3G), and density functional theory (DFT/B3LYP/6-31G*) calculations reveal that these differences in barriers to rotation are the result of differing degrees of hybridization of the non-pyridyl nitrogen in the enantiomerization transition states (TSs). The importance of heteroatom hybridization as a factor in determining nonsteric contributions to barriers to rotation in azabiaryls of this type is discussed.
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| pubmed:language |
eng
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| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
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| pubmed:month |
Nov
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| pubmed:issn |
0022-3263
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| pubmed:author | |
| pubmed:issnType |
Print
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| pubmed:day |
2
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| pubmed:volume |
66
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| pubmed:owner |
NLM
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| pubmed:authorsComplete |
Y
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| pubmed:pagination |
7394-401
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| pubmed:dateRevised |
2003-10-31
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| pubmed:year |
2001
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| pubmed:articleTitle |
Energy barriers to rotation in axially chiral analogues of 4-(dimethylamino)pyridine.
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| pubmed:affiliation |
Department of Chemistry, University of Sheffield, Brook Hill, Sheffield S3 7HF, UK. a.c.spivey@sheffield.ac.uk
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| pubmed:publicationType |
Journal Article
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