Synthesis of a new metal complex bearing N-heterocyclic carbenes and its application to catalytic asymmetric reaction

以手性β-氨基醇为原料，合成了一系列羟基酰胺功能化的氮杂盐，如碘化氮和氯化物。对于氮杂环化合物NHC与钯的配位反应，采用了以NHC-Ag络合物中间体为辅助的配体转移策略。因此，已经成功地合成了多种NHC-Pd络合物。通过单晶X射线衍射研究确定了这些NHC-Pd络合物的详细分子结构。一种手性二聚三齿烷氧基/酰胺/NHC钯(II)络合物在室温下催化芳基硼酸与开环烯烃的Heck式氧化反应，得到具有高对映选择性的偶联产物。

The efficient synthetic routes to a series of hydroxy-amide-functionalized azolium salts such as azolium iodides and chlorides from chiral β-amino alcohols have been developed. For coordination of the azolium compound as NHC to palladium, the strategy based on the ligand transfer with the aid of a NHC-Ag complex intermediate was employed. Thus, a wide variety of NHC-Pd complexes have been successfully synthesized. The detail of the molecular structures of these NHC-Pd complexes was established by single-crystal X-ray diffraction studies. A chiral dimeric tridentate alkoxy/amidate/NHC palladium(II) complex effected oxidative Heck-type reactions of aryl boronic acids with acyclic alkenes at room temperature to afford the corresponding coupling products with high enantioselectivities.