Mode of Activation of Cobalt(II) Amides for Catalytic Hydrosilylation of Alkenes with Tertiary Silanes
作者:Yang Liu、Liang Deng
DOI:10.1021/jacs.6b12938
日期:2017.2.8
capable of catalyzing alkene hydrosilylation in the absence of external activators are rarely known, and their activation mode has remained poorly understood. We present here that cobalt(II) amide complexes, [Co(N(SiMe3)2)2] and its NHC adducts [(NHC)Co(N(SiMe3)2)2] (NHC = N-heterocycliccarbene), are effective catalysts for the hydrosilylation of alkenes with tertiary silanes. Mechanistic studies
在没有外部活化剂的情况下能够催化烯烃氢化硅烷化的钴 (II) 配合物很少为人所知,并且其活化模式仍然知之甚少。我们在此提出钴 (II) 酰胺配合物 [Co(N(SiMe3)2)2] 及其 NHC 加合物 [(NHC)Co(N(SiMe3)2)2](NHC = N-杂环卡宾)是烯烃与叔硅烷氢化硅烷化的有效催化剂。机理研究表明,钴 (II) 酰胺可以与氢硅烷反应形成钴 (I) 物质、甲硅烷基酰胺和氢,作为进入真正催化活性物质的入口,大概是钴 (I) 物质,用于钴催化氢化硅烷化反应。
Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope and Application to Late-Stage Functionalization
Highly efficient and general Ir-catalyzed hydrosilylation of unactivated alkenes with excellent anti-Markovnikov regioselectivity was described. A broad scope of hydrosilylated products were synthesized economically and conveniently from commercially or naturally available compounds, which provides versatile valuable precursors for organic and medicinal studies.