Gao Bao, Zhang Guoying, Zhou Xibing, Huang Hanmin
Department of Chemistry , Hefei National Laboratory for Physical Sciences at the Microscale , University of Science and Technology of China , Hefei , 230026 , P. R. China . Email:
State Key Laboratory for Oxo Synthesis and Selective Oxidation , Lanzhou Institute of Chemical Physics , Chinese Academy of Sciences , Lanzhou 730000 , P. R. China.
Chem Sci. 2017 Oct 24;9(2):380-386. doi: 10.1039/c7sc04054g. eCollection 2018 Jan 14.
Palladium-catalyzed hydroaminocarbonylation of alkenes for the synthesis of primary amides has long been an elusive aim. Here, we report an efficient catalytic system which enables inexpensive NHCl to be utilized as a practical alternative to gaseous ammonia for the palladium-catalyzed alkene-hydroaminocarbonylation reaction. Through appropriate choice of the palladium precursors and ligands, either branched or linear primary amides can be obtained in good yields with good to excellent regioselectivities. Primary mechanistic studies were conducted and disclosed that electrophilic acylpalladium species were capable of capturing the NH-moiety from ammonium salts to form amides in the presence of CO with NMP as a base.
长期以来，钯催化烯烃氢氨羰基化反应合成伯酰胺一直是一个难以实现的目标。在此，我们报道了一种高效催化体系，该体系能使廉价的NHCl作为气态氨的实用替代品，用于钯催化的烯烃氢氨羰基化反应。通过适当选择钯前体和配体，可分别以良好的产率和良好至优异的区域选择性获得支链或直链伯酰胺。我们进行了初步的机理研究，结果表明，在以NMP为碱、CO存在的条件下，亲电酰基钯物种能够从铵盐中捕获NH部分以形成酰胺。
