Organometallic Chemistry Laboratory, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
J Am Chem Soc. 2009 Dec 30;131(51):18266-8. doi: 10.1021/ja909126k.
Various alkynes and alkenes having a tethered ether group undergo methylalumination reactions with unprecedented regio- and stereoselectivity in the presence of a cationic half-sandwich alkylscandium species as a catalyst. The oxygen atom of the ether group plays an important role in controlling the selectivity, possibly by coordinating to the metal center. Even when a bulky tert-butyl(diphenyl)silyloxy group is used as the tether group, there is no loss of selectivity.
各种带有束缚醚基的炔烃和烯烃在阳离子半夹心烷基钪物种作为催化剂的存在下进行甲铝化反应，具有前所未有的区域和立体选择性。醚基的氧原子在控制选择性方面起着重要作用，可能通过与金属中心配位。即使使用大体积的叔丁基（二苯基）硅氧基作为束缚基团，也不会失去选择性。
