Source:http://linkedlifedata.com/resource/pubmed/id/11982371
Switch to
Predicate | Object |
---|---|
rdf:type | |
lifeskim:mentions | |
pubmed:issue |
18
|
pubmed:dateCreated |
2002-5-1
|
pubmed:abstractText |
cis-Stilbene (1) has been epoxidized by a set of diverse oxygen donors [OxD], catalyzed by the Mn(III)(salen)X complexes 3 (X = Cl, PF(6)), to afford a mixture of cis- and trans-epoxides 2. The cis/trans ratios range from 29:71 (extensive isomerization) to 92:8, which depends both on the oxygen source [OxD] and on the counterion X of the catalyst. When (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)-benzene (4) is used as substrate, a mechanistic probe which differentiates between radical and cationic intermediates, no cationic ring-opening products are found in this epoxidation reaction; thus, isomerized epoxide product arises from intermediary radicals. The dependence of the diastereoselectivity on the oxygen source is rationalized in terms of a bifurcation step in the catalytic cycle, in which concerted Lewis-acid-activated oxygen transfer competes with stepwise epoxidation by the established Mn(V)(oxo) species. The experimental counterion effect is attributed to the computationally assessed ligand-dependent reaction profiles and stereoselectivities of the singlet, triplet, and quintet spin states available to the manganese species.
|
pubmed:language |
eng
|
pubmed:journal | |
pubmed:status |
PubMed-not-MEDLINE
|
pubmed:month |
May
|
pubmed:issn |
0002-7863
|
pubmed:author | |
pubmed:issnType |
Print
|
pubmed:day |
8
|
pubmed:volume |
124
|
pubmed:owner |
NLM
|
pubmed:authorsComplete |
Y
|
pubmed:pagination |
5068-73
|
pubmed:dateRevised |
2003-11-3
|
pubmed:year |
2002
|
pubmed:articleTitle |
cis-Stilbene and (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)benzene as mechanistic probes in the Mn(III)(salen)-catalyzed epoxidation: influence of the oxygen source and the counterion on the diastereoselectivity of the competitive concerted and radical-type oxygen transfer.
|
pubmed:affiliation |
Institute of Organic Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany. adam@chemie.uni-wuerzburg.de
|
pubmed:publicationType |
Journal Article
|