| Mechanism and the Origins of Stereospecificity in Copper Catalyzed Ring Expansion of Vinyl Oxiranes: A Traceless Dual Transition Metal-Mediated Process. | |
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MedLine Citation:
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PMID: 23273375 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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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. |
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Authors:
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Thomas J L Mustard; Daniel J Mack; Jon T Njardarson; Paul Ha-Yeon Cheong |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-12-31 |
Journal Detail:
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Title: Journal of the American Chemical Society Volume: - ISSN: 1520-5126 ISO Abbreviation: J. Am. Chem. Soc. Publication Date: 2012 Dec |
Date Detail:
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Created Date: 2012-12-31 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 7503056 Medline TA: J Am Chem Soc Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
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