Iron Catalyzed Asymmetric Hydrogenation of Ketones

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• 作者：Yanyun Li ; Shenluan Yu ; Xiaofeng Wu ; Jianliang Xiao ; Weiyi Shen ; Zhenrong Dong ; Jingxing Gao
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：March 12, 2014
• 年：2014
• 卷：136
• 期：10
• 页码：4031-4039
• 全文大小：503K
• 年卷期：v.136,no.10(March 12, 2014)
• ISSN：1520-5126

文摘

Chiral molecules, such as alcohols, are vital for the manufacturing of fine chemicals, pharmaceuticals, agrochemicals, fragrances, and novel materials. These molecules need to be produced in high yield and high optical purity and preferentially catalytically. Among all the asymmetric catalytic reactions, asymmetric hydrogenation with H₂ (AH) is the most widely used in the industry. With few exceptions, these AH processes use catalysts based on the three critical metals, rhodium, ruthenium, and iridium. Herein we describe a simple, industrially viable iron catalyst that allows for the AH of ketones, a process currently dominated by ruthenium and rhodium catalysts. By combining a chiral, 22-membered macrocyclic ligand with the cheap, readily available Fe₃(CO)₁₂, a wide variety of ketones have been hydrogenated under 50 bar H₂ at 45鈥?5 掳C, affording highly valuable chiral alcohols with enantioselectivities approaching or surpassing those obtained with the noble metal catalysts. In contrast to AH by most noble metal catalysts, the iron-catalyzed hydrogenation appears to be heterogeneous.