Oxidation of Cycloalkenes and Methylenecycloalkanes by Palladium (II) Complexes: Part I. NMR Study on the Mechanism of the Formation of Ring-Contracted and Ring-Opened Products in the Oxidation of 1-Methylcyclobutene Full article
Journal |
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic)
ISSN: 0304-5102 |
||
---|---|---|---|
Output data | Year: 1993, Volume: 83, Number: 3, Pages: 287-300 Pages count : 14 DOI: 10.1016/0304-5102(93)87039-B | ||
Tags | cycloalkene oxidation, methylcyclobutene, methylenecycloalkanes, oxidation, palladium | ||
Authors |
|
||
Affiliations |
|
Abstract:
Oxidation of 1-methylcyclobutene (1) by PdCl2L2 and PdCl(NO2)L2 (LCD3CN) in methylene chloride was studied with 1H and 13C NMR. Reaction of 1 with PdCl2L2 leads to the formation of the stable ring-opened 1-3-η3-π-allyl palladium complex (2). With the addition of an equimolar quantity of PdCl(NO2)L2 to the solution of complex 2, the allylic oxidation of 2 proceeds slowly via the intermediate formation of another 1-3-η3-π-allyl palladium complex (3). When reacting directly with PdCl(NO2)L2, 1 undergoes palladium (II)-catalyzed ring contraction to give cyclopropyl methyl ketone. Kinetic and spectral data indicate the formation of an organometallic intermediate, a product of the β-nitritopalladation of the parent olefin 1.
Cite:
Beck I.E.
, Gusevskaya E.V.
, Golovin A.V.
, Likholobov V.A.
Oxidation of Cycloalkenes and Methylenecycloalkanes by Palladium (II) Complexes: Part I. NMR Study on the Mechanism of the Formation of Ring-Contracted and Ring-Opened Products in the Oxidation of 1-Methylcyclobutene
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1993. V.83. N3. P.287-300. DOI: 10.1016/0304-5102(93)87039-B WOS Scopus РИНЦ
Oxidation of Cycloalkenes and Methylenecycloalkanes by Palladium (II) Complexes: Part I. NMR Study on the Mechanism of the Formation of Ring-Contracted and Ring-Opened Products in the Oxidation of 1-Methylcyclobutene
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1993. V.83. N3. P.287-300. DOI: 10.1016/0304-5102(93)87039-B WOS Scopus РИНЦ
Dates:
Submitted: | Sep 10, 1992 |
Accepted: | Mar 20, 1993 |
Published print: | Jul 30, 1993 |
Published online: | Oct 2, 2001 |
Identifiers:
Web of science | WOS:A1993LQ32700003 |
Scopus | 2-s2.0-0027627787 |
Elibrary | 31642027 |
Chemical Abstracts | 1994:54011 |
Chemical Abstracts (print) | 120:54011 |
OpenAlex | W1533372520 |