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New Bidentate N-Sulfonyl-Substituted Aromatic Amines as Chelate Ligand Backbones: Pd Catalyst Generation in C–C Coupling via In Situ and Precatalyst Modes
Australian Journal of Chemistry ( IF 1.0 ) Pub Date : 2020-07-03 , DOI: 10.1071/ch19668
Hammed Olawale Oloyede , Raymond Akong Akong , Joseph Anthony Orighomisan Woods , Helmar Görls , Winfried Plass , Abiodun Omokehinde Eseola

A series of six new, bidentate ligands based on N-(2-(R-sulfonamido)benzyl)R-sulfonamide have been isolated as dianionic or monoanionic chelators via condensation of 2-(aminomethyl)aniline with sulfonyl chloride reagents; R = methyl (1 and 1′), tolyl (2 and 2′), 2,4,6-trimethylphenyl (3), or 2,4,6-triisopropylphenyl (4). Complexes of ligands 24 reacted at room temperature with palladium(ii) acetate in the presence of various monodentate N-donor co-ligands to form complexes Pd2(2dmap), Pd2′(OAc.py), Pd3(2acn), Pd3(2py), Pd4(2acn), and Pd4(2py), which were structurally confirmed by three X-ray crystal analyses. Results of catalysis studies in water showed high turnover frequencies and yields of up to 98 % within 10 min and at 0.2 mol-% palladium catalyst loading. Relative to ligand-free catalysis in the presence of only Pd(OAc)2, the ligand-supported palladium species clearly possess positive catalytic advantage. Furthermore, Suzuki coupling efficiencies by 1 : 1 ‘Pd(OAc)2 + ligand’ yielded notably better outcomes than for the 1 : 2 ‘Pd(OAc)2 + ligand’ in situ catalyst generation, which reveals that coordinative saturation is undesirable. The size of the complementing monodentate co-ligand was observed to influence the catalytic efficiency such that bulkier co-ligands consistently yielded improved turnover frequency values, which leads to the conclusion that steric repulsion between the synthesised ligands and the bulkier co-ligands aided the generation of vacant coordination sites for the more active complexes. Moderate Heck coupling activity was recorded for the complexes and better activities appear to correlate with moderate bulkiness of ligand 3.



中文翻译:

新型双齿N-磺酰基取代的芳香胺作为螯合配体骨架:通过原位和预催化方式在C-C偶联中生成Pd催化剂

通过2-(氨基甲基)苯胺与磺酰氯试剂的缩合,分离出一系列基于N-(2-(R-磺酰胺基)苄基)R-磺酰胺的六个新的双齿配体作为阴离子或单阴离子螯合剂。R =甲基(11'),甲苯基(22'),2,4,6-三甲基苯基(3)或2,4,6-三异丙基苯基(4)。配位体的配合物2 - 4在室温下用钯反应(II在不同的单齿N-供共配体的存在下形成)乙酸乙酯配合物加入Pd 2(2dmap),加入Pd 2'(OAc.py),器Pd3(2acn),Pd3(2py),Pd4(2acn)和Pd4(2py),通过三个X射线晶体分析在结构上得到确认。在水中进行的催化研究结果表明,在钯催化剂负载量为0.2 mol%的情况下,在10分钟内高转换频率和高达98%的产率。相对于仅存在Pd(OAc)2的无配体催化,配体负载的钯物质显然具有积极的催化优势。此外,通过铃木偶联1的效率:1 '的Pd(OAC)2  +配体'显着产生优于为1的结果:2“的Pd(OAC)2 +配体'原位催化剂的产生,这表明配位饱和是不希望的。观察到互补的单齿共配体的尺寸影响催化效率,从而较大的共配体持续产生改善的周转频率值,这得出结论,合成的配体和较大的共配体之间的空间排斥有助于生成。较活跃的复合体的空缺协调站点。记录到适度的Heck偶联活性的配合物和更好的活动似乎与适度的配体3相关

更新日期:2020-08-20
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