Nagasawa Shota, Sasano Yusuke, Iwabuchi Yoshiharu
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, Japan.
Chemistry. 2017 Aug 1;23(43):10276-10279. doi: 10.1002/chem.201702512. Epub 2017 Jul 12.
The first catalytic oxygenative allylic transposition of unactivated alkenes into enones has been developed using an oxoammonium salt as the catalyst. This reaction converts various tri- and trans-disubstituted alkenes into their corresponding enones with transposition of their double bonds at ambient temperature in good yields. The use of a less-hindered azaadamantane-type oxoammonium salt as the catalyst and a combination of two distinct stoichiometric oxidants, namely, iodobenzene diacetate and magnesium monoperoxyphthalate hexahydrate (MMPP⋅6 H O) are essential to facilitate the enone formation efficiently.
利用氧鎓盐作为催化剂，首次实现了未活化烯烃向烯酮的催化氧化烯丙基转位反应。该反应在室温下将各种三取代和反式二取代烯烃转化为相应的烯酮，双键发生转位，产率良好。使用空间位阻较小的氮杂金刚烷型氧鎓盐作为催化剂，以及两种不同的化学计量氧化剂（即二醋酸碘苯和六水合单过氧邻苯二甲酸镁（MMPP·6H₂O））的组合，对于有效促进烯酮的形成至关重要。
