Mechanistic Insights into Grubbs-Type Ruthenium-Complex-Catalyzed Intramolecular Alkene Hydrosilylation: Direct σ-Bond Metathesis in the Initial Stage of Hydrosilylation
作者:Apparao Bokka、Yuanda Hua、Adam S. Berlin、Junha Jeon
DOI:10.1021/acscatal.5b00431
日期:2015.6.5
synthesis of organosilicon heterocycles from readily available olefins, this study provides fundamental mechanistic insights into the non-metathetical function of Grubbs-type ruthenium catalysts. In the initial stage of hydrosilylation within a ruthenium coordination sphere, evidence for activation of a ruthenium complex by direct σ-bond metathesis between Si–H and Ru–Cl via a four-centered transition state
已经开发了Grubbs型钌配合物介导的烯基甲硅烷基醚的分子内烯烃氢化硅烷化以提供具有高区域选择性的环状甲硅烷基醚。值得注意的是,这种钌配合物通过非Si-H键活化而不是烯烃活化而非金属地用于烯烃氢化硅烷化反应,在这种情况下,未检测到竞争的烯烃复分解二聚作用。除了从容易获得的烯烃合成有机硅杂环化合物之外,本研究还提供了有关Grubbs型钌催化剂的非复分解功能的基本机理的见解。在钌配位范围内的氢化硅烷化的初始阶段,提出了通过四中心过渡态通过Si–H和Ru–Cl之间的直接σ键复分解来活化钌配合物的证据。3 Si–H穿过Ru-亚苄基的π键。