Mechanism of SmI <subscript>2</subscript> Reduction of 5-Bromo-6-oxo-6-phenylhexyl Methanesulfonate Studied by Spin Trapping with 2-Methyl-2-nitrosopropane. - OpacWWW

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Tytuł:: Mechanism of SmI 2 Reduction of 5-Bromo-6-oxo-6-phenylhexyl Methanesulfonate Studied by Spin Trapping with 2-Methyl-2-nitrosopropane.
Autorzy:: Aretz CD; Department of Chemistry and Biochemistry , University of Denver , Denver , Colorado 80208 , United States.
McPeak JE; Department of Chemistry and Biochemistry , University of Denver , Denver , Colorado 80208 , United States.
Eaton GR; Department of Chemistry and Biochemistry , University of Denver , Denver , Colorado 80208 , United States.
Eaton SS; Department of Chemistry and Biochemistry , University of Denver , Denver , Colorado 80208 , United States.
Cowen BJ; Department of Chemistry and Biochemistry , University of Denver , Denver , Colorado 80208 , United States.
Źródło:: The Journal of organic chemistry [J Org Chem] 2018 Sep 07; Vol. 83 (17), pp. 10688-10692. Date of Electronic Publication: 2018 Aug 23.
Typ publikacji:: Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, Non-P.H.S.
Język:: English
Imprint Name(s):: Publication: Columbus Oh : American Chemical Society
Original Publication: Easton, Pa. [etc.]
MeSH Terms:: Spin Trapping*
Iodides/*chemistry
Nitroso Compounds/*chemistry
Samarium/*chemistry
Sulfonic Acids/*chemistry
Electron Spin Resonance Spectroscopy ; Oxidation-Reduction
Grant Information:: R01 CA177744 United States CA NCI NIH HHS; CHE-1227992 International National Science Foundation
Substance Nomenclature:: 0 (Iodides)
0 (Nitroso Compounds)
0 (Sulfonic Acids)
42OD65L39F (Samarium)
JGX6N17V2U (tert-nitrosobutane)
L15T8U41LC (samarium diiodide)
Entry Date(s):: Date Created: 20180814 Date Completed: 20190916 Latest Revision: 20190916
Update Code:: 20240104
DOI:: 10.1021/acs.joc.8b01517
PMID:: 30102044
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The radical formed by reduction of 5-bromo-6-oxo-6-phenylhexyl methanesulfonate, an α-bromoketone, with SmI 2 was spin trapped with 2-methyl-2-nitrosopropane. Electron paramagnetic resonance spectra of the spin adduct and the adduct formed in the analogous reaction with selectively deuterated substrate identify the radical intermediate in this SmI 2 reduction as a carbon-centered radical. This result supports the proposal that the formation of reactive Sm-enolates arises from reduction of the carbon-bromine bond rather than a ketyl radical anion.

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Mechanism of SmI 2 Reduction of 5-Bromo-6-oxo-6-phenylhexyl Methanesulfonate Studied by Spin Trapping with 2-Methyl-2-nitrosopropane.