Kim Mansuk, Park Sangho, Maifeld Sarah V, Lee Daesung
Department of Chemistry, University of Wisconsin, Madison, WI 53706, USA.
J Am Chem Soc. 2004 Aug 25;126(33):10242-3. doi: 10.1021/ja0465909.
Cross metathesis between silylalkynes and various functionalized alkenes catalyzed by Grubbs carbene complex produced, in most cases, single regio- and stereoisomers of the resultant 1,3-dienes. Polar heteroatom substituents at the propargylic site are important for high reactivity and selectivity. An important mechanistic insight regarding the initiation event and the key propagating alkylidene in this reaction was obtained by employing a tandem cross metathesis ring-closing metathesis between a terminal alkene and a silylated alkyne possessing an alkene tether.
在大多数情况下，由格拉布卡宾配合物催化的硅烷基炔烃与各种官能化烯烃之间的交叉复分解反应生成了所得1,3 - 二烯的单一区域和立体异构体。炔丙基位点的极性杂原子取代基对于高反应性和选择性很重要。通过在末端烯烃与具有烯烃连接基的硅烷基化炔烃之间进行串联交叉复分解-闭环复分解反应，获得了关于该反应引发事件和关键传播亚烷基的重要机理见解。
