Efficient Hydrosilylation of Acetophenone with a New Anthraquinonic Amide-Based Iron Precatalyst

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• 作者：Álvaro Raya-Barón ; Manuel A. Ortuño ; Pascual Oña-Burgos ; Antonio Rodríguez-Diéguez ; Robert Langer ; Christopher J. CramerIstemi Kuzu ; Ignacio Fernández
• 刊名：Organometallics
• 出版年：2016
• 出版时间：December 27, 2016
• 年：2016
• 卷：35
• 期：24
• 页码：4083-4089
• 全文大小：444K
• ISSN：1520-6041

文摘

A new iron complex based on a noninnocent anthraquinonic ligand has been synthesized and fully characterized through multiple techniques, including NMR, X-ray crystallography, mass spectrometry, and cyclic voltammetry. Exposure of ketone to that complex in the presence of (EtO)₂MeSiH affords the corresponding silylated alcohol. Loadings as low as 0.25 mol % afford excellent yields at room temperature. Quantum–chemical analysis of the catalytic mechanism supports activation of the precatalyst to form a Fe–hydride intermediate, followed by ketone reduction and σ-bond metathesis.