Feb, 2006
Enantioselective photooxidation of a sulfide by a chiral ruthenium(II) complex immobilized on a montmorillonite clay surface: The role of weak interactions in asymmetric induction
JOURNAL OF PHYSICAL CHEMISTRY B
- ,
- ,
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- Volume
- 110
- Number
- 6
- First page
- 2533
- Last page
- 2540
- Language
- English
- Publishing type
- Research paper (scientific journal)
- DOI
- 10.1021/jp055254r
- Publisher
- AMER CHEMICAL SOC
The present work pursued a possibility that enantioselectivity was achieved through weak intermolecular interactions between a catalyst and a substrate. For that purpose, we Studied the photooxidation of alpha-ethylbenzyl phenyl sulfide catalyzed by a polypyridyl ruthenium(II) complex as a chiral photosensitizer. No covalent bonding was formed between a catalyst and a substrate, because the complexes used ([Ru(phen)(3)](2+) or [Ru(bpY(3))(2+)]) were coordinatively saturated. Enantiomer excess (ee) was attained to be 30% when a chiral photosensitizer was immobilized on montmorillonite clay. It was even improved to 43% in the presence of an additional chiral auxiliary, dibenzoyl-(D)(+)-tartaric acid. Notably, no enantioselectivity was achieved when the reaction took place in homogeneous solutions. The ab initio calculations were performed on the stability of an associate composed of a catalyst (metal complex) and a product (sulfoxide) to obtain a clue to reaction mechanisms. The calculations suggest that chiral discrimination is achieved even through noncovalent interactions between a substrate and a chiral senstizer when the attacking direction by a substrate toward a catalyst is limited sterically on a solid surface.
- Link information
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- DOI
- https://doi.org/10.1021/jp055254r
- Web of Science
- https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000235373400014&DestApp=WOS_CPL
- URL
- http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=33644760839&origin=inward
- ID information
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- DOI : 10.1021/jp055254r
- ISSN : 1520-6106
- SCOPUS ID : 33644760839
- Web of Science ID : WOS:000235373400014