Acceleration Effect of an Allylic Hydroxy Group on Ring-Closing Enyne Metathesis of Terminal Alkynes: Scope, Application, and Mechanistic Insights
作者:Tatsushi Imahori、Hidetomo Ojima、Yuichi Yoshimura、Hiroki Takahata
DOI:10.1002/chem.200801439
日期:——
acceleration effect of an allylic hydroxy group on ring-closing enyne metathesis has been found. Ring-closing enyne metathesis of terminal alkynes possessing an allylic hydroxy group proceeded smoothly without the ethylene atmosphere generally necessary to promote the reaction. The synthesis of (+)-isofagomine with the aid of this efficient reaction has been demonstrated. Mechanistic studies of the acceleration
已经发现烯丙基羟基对闭环烯炔复分解的有趣的加速作用。具有烯丙基羟基的末端炔烃的闭环烯炔复分解反应顺利进行,而通常没有促进反应所需的乙烯气氛。已经证明了借助该有效反应的(+)-异黄花碱的合成。还进行了加速作用的机理研究。NMR研究的结果表明反应是通过“烯-然后-炔”途径进行的。动力学研究表明,由于存在烯丙基羟基,导致速率确定步骤的切换。这些结果表明,烯丙基羟基加速了Ru-卡宾物质的再进入步骤。