Ji Xiaolei, Gao Bao, Zhou Xibing, Liu Zongjian, Huang Hanmin
College of Chemical Engineering , Zhejiang University of Technology , Hangzhou 310024 , China.
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry , Center for Excellence in Molecular Synthesis, University of Science and Technology of China, Chinese Academy of Sciences , Hefei 230026 , P.R. China.
J Org Chem. 2018 Sep 7;83(17):10134-10141. doi: 10.1021/acs.joc.8b01405. Epub 2018 Jul 10.
α,β-Unsaturated primary amides have found numerous applications in drug development, organic materials, and polymer sciences. However, the catalytic synthesis of α,β-unsaturated primary amides via carbonylation of alkynes has long been an elusive endeavor. Here, we report a novel palladium-catalyzed hydroaminocarbonylation of alkynes with NHCl as the amine source, enabling the highly chemo- and regioselective synthesis of α,β-unsaturated primary amides. A variety of alkynes, including aromatic alkynes, aliphatic alkynes, terminal alkynes, internal alkynes, as well as diynes with various functional groups, react well. The method turns the parasitic noncoordination ability of ammonium salts into a strategic advantage, enabling the gram-scale reaction to be performed in the presence of 0.05 mol % of catalyst with excellent selectivity.
α,β-不饱和伯酰胺在药物开发、有机材料和聚合物科学领域有诸多应用。然而，通过炔烃羰基化催化合成α,β-不饱和伯酰胺长期以来一直是一项难以实现的工作。在此，我们报道了一种以NHCl为胺源的新型钯催化炔烃氢胺羰基化反应，可实现α,β-不饱和伯酰胺的高度化学和区域选择性合成。各种炔烃，包括芳炔、脂肪炔、端炔、内炔以及带有各种官能团的二炔，都能很好地反应。该方法将铵盐的寄生性非配位能力转化为战略优势，使得在0.05 mol%催化剂存在下能进行克级规模反应，且选择性优异。
