Over the past two decades,homogeneous gold catalysis has experienced exponential development and contributed a plethora of highly valuable synthetic methods to the synthetic toolbox.Metal–ligand cooperative catalysis...Over the past two decades,homogeneous gold catalysis has experienced exponential development and contributed a plethora of highly valuable synthetic methods to the synthetic toolbox.Metal–ligand cooperative catalysis is a versatile strategy for achieving highly efficient and/or novel catalysis but has seldom been explored in gold chemistry.This minireview summarizes the progress we have made in developing remotely functionalized biaryl-2-ylphosphine ligands and employing them in cooperative gold catalysis that achieves excellent catalytic efficiency or realizes previously unknown reactivities.This approach also provides new venues for implementing asymmetric gold catalysis.展开更多
A series of clip-shaped cationic molecular corners C1~C4(C1=[(bpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C2=[(dmbpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C3=(bpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),C4=(dmbpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),bpy=2,2-bi...A series of clip-shaped cationic molecular corners C1~C4(C1=[(bpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C2=[(dmbpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C3=(bpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),C4=(dmbpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),bpy=2,2-bipyridine,dmbpy=4,4΄-dimethyl-2,2-bipyridine)were synthesized through dipalladium complexes[(bpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2),[(dmbpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2)and bifunctional pyrazole ligands 4-(3,4-dimethoxyphenyl)-3,5-dimethyl-1H-pyrazol(HL^(1))and 4,4΄-(5-(^(1)H-pyrazol-4-yl)-1,3-phenylene)dipyridine(HL^(2)).Complexes C1~C4 were characterized by^(1)H and^(13)C NMR,electrospray ionization mass spectrometry(ESI-MS),elemental analysis,and IR spectroscopy.The X-ray diffraction analysis of C1∙2NO_(3)−revealed a Pd_(2)dimetallic clip-shaped structure which was synthesized by two bifunctional ligands doubly bridged by the[(bpy)Pd]_(2)dimetal units.Additionally,all of the complexes with NO_(3)−as counter anions exhibited high-efficiency catalytical performance in the Suzuki-coupling reaction attributed to the tunable impact and weak dinuclear Pd(Ⅱ)···Pd(Ⅱ)intramolecular bonding interaction.展开更多
基金supported by the National Science Foundation,Division of Chemistry(NSF CHE 1800525).
文摘Over the past two decades,homogeneous gold catalysis has experienced exponential development and contributed a plethora of highly valuable synthetic methods to the synthetic toolbox.Metal–ligand cooperative catalysis is a versatile strategy for achieving highly efficient and/or novel catalysis but has seldom been explored in gold chemistry.This minireview summarizes the progress we have made in developing remotely functionalized biaryl-2-ylphosphine ligands and employing them in cooperative gold catalysis that achieves excellent catalytic efficiency or realizes previously unknown reactivities.This approach also provides new venues for implementing asymmetric gold catalysis.
基金the Beijing Natural Science Foundation of China(2212002)National Natural Science Foundation of China(21906002,21471011)+2 种基金the Beijing Municipal Science and Technology Project(KM202010005010)the Beijing Municipal High Level Innovative Team Building Program(IDHT20180504)the Beijing Outstanding Young Scientist Program(BJJWZYJH01201910005017)。
文摘A series of clip-shaped cationic molecular corners C1~C4(C1=[(bpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C2=[(dmbpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C3=(bpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),C4=(dmbpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),bpy=2,2-bipyridine,dmbpy=4,4΄-dimethyl-2,2-bipyridine)were synthesized through dipalladium complexes[(bpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2),[(dmbpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2)and bifunctional pyrazole ligands 4-(3,4-dimethoxyphenyl)-3,5-dimethyl-1H-pyrazol(HL^(1))and 4,4΄-(5-(^(1)H-pyrazol-4-yl)-1,3-phenylene)dipyridine(HL^(2)).Complexes C1~C4 were characterized by^(1)H and^(13)C NMR,electrospray ionization mass spectrometry(ESI-MS),elemental analysis,and IR spectroscopy.The X-ray diffraction analysis of C1∙2NO_(3)−revealed a Pd_(2)dimetallic clip-shaped structure which was synthesized by two bifunctional ligands doubly bridged by the[(bpy)Pd]_(2)dimetal units.Additionally,all of the complexes with NO_(3)−as counter anions exhibited high-efficiency catalytical performance in the Suzuki-coupling reaction attributed to the tunable impact and weak dinuclear Pd(Ⅱ)···Pd(Ⅱ)intramolecular bonding interaction.
