Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University , Beijing 100084, China.
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology , Hangzhou 310014, China.
J Am Chem Soc. 2016 Jul 13;138(27):8588-94. doi: 10.1021/jacs.6b04271. Epub 2016 Jun 30.
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.
在此，我们报告了一种新型的钴催化的炔烃对 Z-和 E-烯烃的立体选择性转移氢化反应。通过合理的催化剂设计实现了有效的选择性控制。此外，该温和的体系可以使用低至 0.2 mol%的催化剂负载量，以良好的收率实现带有广泛官能团的炔烃的转移氢化。该方法的通用性通过合成 50 多种具有良好化学和立体选择性的烯烃得到了突出体现。初步的机理研究表明，E-烯烃产物是通过炔烃的顺序氢化生成 Z-烯烃中间体，然后再进行 Z 到 E 的烯烃异构化过程生成的。
