Oxidation of Cycloalkenes and Methylenecycloalkanes by Palladium(II) Complexes. Part 2. NMR Study on the Mechanism of the Ring Expansion of Methylenecyclobutane
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| 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: 301-310
Pages count
: 10
DOI:
10.1016/0304-5102(93)87040-F
|
| Tags |
cycloalkene oxidation, methylenecyclobutane, oxidation, palladium |
| Authors |
Beck I.E.
1
,
Gusevskaya E.V.
1
,
Golovin A.V.
1
,
Likholobov V.A.
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis
|
|
The reaction of methylenecyclobutane (1) with bis(acetonitrile)chloronitropalladium(II) in methylene chloride yields cyclopentanone. Two intermediates - π-olefin complex of palladium and product of β-nitritopalladation of 1 in a Markovnikov fashion - are observed by 1H and 13C NMR. Palladium-catalyzed ring expansion of 1 is suggested to involve heterolysis of the palladium-carbon bond and rearrangement of the resulting cyclobutyl to cyclopentyl cations. The selective formation of ring-expanded and ring-contracted carbonyl products from methylenecyclobutane and
1-methyleyclobutene, respectively, is discussed in terms of proposed mechanism.