Source:http://linkedlifedata.com/resource/pubmed/id/11971726
Switch to
| Predicate | Object |
|---|---|
| rdf:type | |
| lifeskim:mentions | |
| pubmed:issue |
17
|
| pubmed:dateCreated |
2002-4-24
|
| pubmed:abstractText |
The compound [Ru(salen)(NO)(H(2)O)](SbF(6)) (1) (salen = N,N'-ethylene-bis-salicylidene aminate) reacts catalytically with thiiranes and converts them to olefins and 1,2,3,4-tetrathianes or 1,2,3-trithiolanes. The monosubstituted thiiranes styrene sulfide and propylene sulfide reacted to form the corresponding olefin and the 4-substituted 1,2,3-trithiolane in a 2:1 ratio in isolated yields in excess of 90%. The disubstituted thiirane cis-stilbene sulfide was converted to cis-stilbene and 5,6-trans-1,2,3,4-diphenyltetrathiane in a 3:1 ratio in the presence of a catalytic amount of 1 in CD(3)NO(2). Coordination of cis-stilbene sulfide to the salen complex in a ligand substitution reaction was established by isolation of [Ru(salen)(NO)(cis-stilbene sulfide)](SbF(6)) (6). (1)H NMR studies performed on 6 indicated that the salen macrocycle had rearranged upon thiirane coordination. A similar rearrangement was found to be stabilized by other ligands including tetramethylethylene sulfide, tetrahydrothiophene, and d(3)-acetonitrile. The alpha-deuterio-cis-stilbene sulfide catalyst adduct (d-6) reacted with unlabeled cis-stilbene sulfide to form deuterium-labeled trans-diphenyl-tetrathiane and unlabeled cis-stilbene as shown by GCMS and (1)H NMR. Thus, the solution thiirane behaves as a sulfur donor and forms olefin, whereas the coordinated thiirane becomes the cyclic polysulfide. beta-cis-Deuteriostyrene sulfide was used to show that ring closure to form cyclic polysulfide incorporated inversion of stereochemistry versus starting thiirane. A mechanism for catalysis consistent with experimental data is presented that requires coordination of thiirane to the metal complex followed by bimolecular attack of free thiirane on the coordinated thiirane.
|
| pubmed:language |
eng
|
| pubmed:journal | |
| pubmed:status |
PubMed-not-MEDLINE
|
| pubmed:month |
May
|
| pubmed:issn |
0002-7863
|
| pubmed:author | |
| pubmed:issnType |
Print
|
| pubmed:day |
1
|
| pubmed:volume |
124
|
| pubmed:owner |
NLM
|
| pubmed:authorsComplete |
Y
|
| pubmed:pagination |
4770-8
|
| pubmed:dateRevised |
2003-11-3
|
| pubmed:year |
2002
|
| pubmed:articleTitle |
Synthesis of trithiolanes and tetrathianes from thiiranes catalyzed by ruthenium salen nitrosyl complexes.
|
| pubmed:affiliation |
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
|
| pubmed:publicationType |
Journal Article
|