Document Detail


Mechanism and the Origins of Stereospecificity in Copper Catalyzed Ring Expansion of Vinyl Oxiranes: A Traceless Dual Transition Metal-Mediated Process.
MedLine Citation:
PMID:  23273375     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
Density functional theory computations of the Cu-catalyzed ring expansion of vinyloxiranes is mediated by a traceless dual Cu(I)-catalyst mechanism. Overall, the reaction involves a monomeric Cu(I)-catalyst, but a single key step, the Cu migration, requires two Cu(I)-catalysts for the transformation. This dual-Cu step is found to be a true two Cu(I)-transition state rather than a mono Cu(I)-transition state in the presence of an adventitious, spectator Cu(I). Both Cu(I) catalysts are involved in the bond forming and breaking process. The single Cu(I) transition state is not a stationary point on the potential energy surface. Interestingly, the reductive elimination is rate-determining for the major diastereomeric product, while the Cu(I)-migration step is rate-determining for the minor. Thus, while the reaction requires dual Cu(I)-activation to proceed, kinetically, the presence of the dual-Cu(I) step is untraceable. The diastereospecificity of this reaction is controlled by the Cu migration step. Suprafacial migration is favored over antarafacial migration due to the distorted Cu π-allyl in the latter.
Authors:
Thomas J L Mustard; Daniel J Mack; Jon T Njardarson; Paul Ha-Yeon Cheong
Related Documents :
24616015 - Ruthenium-catalyzed c7 amidation of indoline ch bonds with sulfonyl azides.
23592625 - Strikingly dissimilar effect of mn and zn dopants imposed on local structural distortio...
24436015 - A donor-stabilized zwitterionic "half-parent" phosphasilene and its unusual reactivity ...
24109385 - 2-(benz-yloxy)iso-quinoline-1,3(2h,4h)-dione.
21322115 - Facile preparation of homo- and hetero-dimetallic complexes with a 4-phosphino-substitu...
18331035 - Construction of a chiral quaternary carbon center by indium-catalyzed asymmetric alpha-...
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-12-31
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  -     ISSN:  1520-5126     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2012 Dec 
Date Detail:
Created Date:  2012-12-31     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Export Citation:
APA/MLA Format     Download EndNote     Download BibTex
MeSH Terms
Descriptor/Qualifier:

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


Previous Document:  The duration of SIRS before organ failure is a significant prognostic factor of sepsis.
Next Document:  Highly enantioselective oxidation of ?-hydroxyacids bearing a substituent with an aryl group: Co-pro...