Mechanistic Insight into the (NHC)copper(I)-Catalyzed Hydrosilylation of Ketones

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• 作者：Thomas Vergote ; Fady Nahra ; Alain Merschaert ; Olivier Riant ; Daniel Peeters ; Tom Leyssens
• 刊名：Organometallics
• 出版年：2014
• 出版时间：April 28, 2014
• 年：2014
• 卷：33
• 期：8
• 页码：1953-1963
• 全文大小：453K
• 年卷期：v.33,no.8(April 28, 2014)
• ISSN：1520-6041

文摘

(NHC)copper(I) hydride catalyzed ketone hydrosilylation is an efficient method for the enantioselective synthesis of secondary alcohols. Herein, we represent a computational study of this reaction using density functional theory (DFT) on realistic model systems. This study is supported by kinetic investigations, using in situ FTIR measurements. The calculations validate the previously proposed reaction mechanism and explain the high activity of (OR¹)_xR²_3鈥?i>xSi鈥揌 types of silanes. Experimental evidence in favor of the monomeric (NHC)CuH form of the catalyst is also given. Combining experimental and theoretical results furthermore highlights a Lewis base activation of the hydrosilane, leading to a modified suggestion for the mechanistic scheme of the catalytic cycle.