Nishimura T, Ohe K, Uemura S
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
J Org Chem. 2001 Feb 23;66(4):1455-65. doi: 10.1021/jo0016475.
Palladium(II)-catalyzed oxidative reaction of tert-cyclobutanols involving the cleavage of a C-C bond via beta-carbon elimination under atmospheric pressure of oxygen is described. An alkylpalladium intermediate produced by beta-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.
描述了钯（II）催化的叔环丁醇氧化反应，该反应在氧气常压下通过β-碳消除涉及C-C键的断裂。由Pd（II）醇盐经β-碳消除产生的烷基钯中间体根据环丁烷环上的取代基给出多种产物，其中涉及脱氢开环、扩环和缩环等反应。对于一些底物，加入催化量的丙烯酸乙酯会显著加速反应。在所有情况下，均获得脱氢产物，并且在最后阶段产生的Pd（II）-氢化物物种可通过分子氧再次转化为活性Pd（II）物种。
