Asymmetric Catalysis with an Inert Chiral-at-Metal Iridium Complex

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• 作者：Liang-An Chen ; Weici Xu ; Biao Huang ; Jiajia Ma ; Lun Wang ; Jianwei Xi ; Klaus Harms ; Lei Gong ; Eric Meggers
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：July 24, 2013
• 年：2013
• 卷：135
• 期：29
• 页码：10598-10601
• 全文大小：241K
• 年卷期：v.135,no.29(July 24, 2013)
• ISSN：1520-5126

文摘

The development of a chiral-at-metal iridium(III) complex for the highly efficient catalytic asymmetric transfer hydrogenation of 尾,尾鈥?disubstituted nitroalkenes is reported. Catalysis by this inert, rigid metal complex does not involve any direct metal coordination but operates exclusively through weak interactions with functional groups properly arranged in the ligand sphere of the iridium complex. Although the iridium complex relies only on the formation of three hydrogen bonds, it exceeds the performance of most organocatalysts with respect to enantiomeric excess (up to 99% ee) and catalyst loading (down to 0.1 mol %). This work hints at an advantage of structurally complicated rigid scaffolds for non-covalent catalysis, which especially relies on conformationally constrained cooperative interactions between the catalyst and substrates.