Advancing the Mechanistic Understanding of an Enantioselective Palladium-Catalyzed Alkene Difunctionalization Reaction.
The mechanism of an enantioselective palladium-catalyzed alkene difunctionalization reaction has been investigated. Kinetic analysis provides evidence of turnover-limiting attack of a proposed quinone methide intermediate with MeOH and suggests that copper is involved in productive product formation...
| Published in: | Journal of the American Chemical Society Vol. 132; no. 49; pp. 17471 - 17483 |
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| Main Authors: | , , |
| Format: | Article |
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American Chemical Society
12/15/2010
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| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=56659039&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 56659039 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/15/2010 vid: 132 iid: 49 pid: 997 pub: American Chemical Society artinfo: ui: 56659039 10.1021/ja108106h ppf: 17471 ppct: 12 formats: tig: atl: Advancing the Mechanistic Understanding of an Enantioselective Palladium-Catalyzed Alkene Difunctionalization Reaction. aug: au: Jensen, Katrina H. Webb, Jonathan D. Sigman, Matthew S. affil: Departments of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, United States Queen's University, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada su: Enantioselective catalysis Ligands (Chemistry) Substrates (Materials science) Quantum perturbations Biocomplexity Palladium catalysts Alkenes sug: subj: Enantioselective catalysis Ligands (Chemistry) Substrates (Materials science) Quantum perturbations Biocomplexity Palladium catalysts Alkenes ab: The mechanism of an enantioselective palladium-catalyzed alkene difunctionalization reaction has been investigated. Kinetic analysis provides evidence of turnover-limiting attack of a proposed quinone methide intermediate with MeOH and suggests that copper is involved in productive product formation, not just catalyst turnover. Through examination of substrate electronic effects, a Jaffé relationship was observed correlating rate to electronic perturbation at two positions of the substrate. Ligand effects were evaluated to provide evidence of rapid ligand exchange between palladium and copper as well as a correlation between ligand electronic nature and enantioselectivity. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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