Ligand-Controlled Cobalt-Catalyzed Transfer Hydrogenation of Alkynes: Stereodivergent Synthesis of Z- and E-Alkenes

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• 作者：Shaomin Fu ; Nan-Yu Chen ; Xufang Liu ; Zhihui Shao ; Shu-Ping Luo ; Qiang Liu
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：July 13, 2016
• 年：2016
• 卷：138
• 期：27
• 页码：8588-8594
• 全文大小：486K
• 年卷期：0
• ISSN：1520-5126

文摘

Herein, we report a novel cobalt-catalyzed stereodivergent transfer hydrogenation of alkynes to Z- and E-alkenes. Effective selectivity control is achieved based on a rational catalyst design. Moreover, this mild system allows for the transfer hydrogenation of alkynes bearing a wide range of functional groups in good yields using catalyst loadings as low as 0.2 mol %. The general applicability of this procedure is highlighted by the synthesis of more than 50 alkenes with good chemo- and stereoselectivity. A preliminary mechanistic study revealed that E-alkene product was generated via sequential alkyne hydrogenation to give Z-alkene intermediate, followed by a Z to E alkene isomerization process.