Oxidative transformation of tert-cyclobutanols by palladium catalysis under oxygen atmosphere

被引:92
作者
Nishimura, T [1 ]
Ohe, K [1 ]
Uemura, S [1 ]
机构
[1] Kyoto Univ, Grad Sch Engn, Dept Energy & Hydrocarbon Chem, Sakyo Ku, Kyoto 6068501, Japan
关键词
D O I
10.1021/jo0016475
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Palladium(II)-catalyzed oxidative reaction of tert-cyclobutanols involving the cleavage of a C-C bond via P-carbon elimination under atmospheric pressure of oxygen is described. An alkylpalladium intermediate produced by P-carbon elimination from a Pd(II) alcoholate gives a variety of products, depending on the substituents on the cyclobutane ring, in which reactions such as dehydrogenative ring opening, ring expansion and ring contraction are involved. For some substrates, the addition of a catalytic amount of ethyl acrylate dramatically accelerates the reaction. In all cases, the dehydrogenative products are obtained and the Pd(II)-hydride species produced at the final stage can be converted again to active Pd(II) species by molecular oxygen.
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收藏
页码:1455 / 1465
页数:11
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