钯/硫酰胺配体催化下Csp~2-Csp~2交叉偶联反应
河南省科学院质量检验与分析测试研究中心 河南省化工研究所有限责任公司
2014-10-26
钯 硫酰胺 芳基碘 芳基锌试剂 交叉偶联
Pd(CH3CN)2Cl2与硫酰胺配体形成的金属络合物为催化剂应用到Csp2-Csp2成键的Negishi(根岸英一)偶联反应中去,发现此催化体系不但反应速度很快,并且催化剂的量比例比较小,这说明反应效率比较高.当使用苯基锌试剂与对碘苯甲酸乙酯的反应时,发现催化体系TON值可以达到105,并且代物催化体系对溴化物的兼容性相对较好,在室温下就能对溴代物和碘代物很好的分离.在通过筛选条件之后,发现对溴的选择性可以达到90%以上.并且,对氯代物的兼容性研究发现,采用同样的方法可以达到97%以上.%The metal complexes of Pd(CH3CN)2Cl2 and sulfur amide ligands as the catalyst was applied to theCsp2-Csp2 negishi bond formation coupling reactions. It was found that the reaction speed was very fast,and theamount of catalyst ratio was relatively small,suggesting that the reaction efficiency was relatively high. The TON ofthe reaction of ethylp-iodobenzoate with phenylzinc reagent was up to 105. Furthermore,bromo groups were welltolerated in the catalytic system. The selectivity for an iodo group in the presence of a bromo group was up to 90%.The selectivity for an iodo group in the presence of a chloro group was up to 97% under the same conditions.
