Pd^(Ⅱ)催化的芳基次膦酸衍生物C—H键活化芳基化反应及衍生化反应  

Pd^(Ⅱ)-Catalyzed C—H Arylation of Aryl Phosphonic Acid Derivatives and the Derivatization Reaction of the Coupled Products

作　　者：关静[1,2] 吴国杰[3] 韩福社[1] 

机构地区：[1]中国科学院长春应用化学研究所,长春130022 [2]中国科学院大学,北京100864 [3]东北师范大学化学系,长春130024

出　　处：《应用化学》2014年第11期1280-1289,共10页Chinese Journal of Applied Chemistry

摘　　要：通过对钯催化的不同次膦酸衍生物芳基偶联反应的深入探索,发现在Pd(OAc)2作催化剂,Ag2CO3作氧化剂,对苯醌(BQ)作添加剂的反应条件下,可以高效地实现芳基次膦酰胺邻位C—H键的直接芳基化。机理研究表明,芳基次膦酰胺邻位C—H键活化芳基偶联反应经历了Pd(0)到Pd(Ⅱ)的催化循环。在对偶联产物衍生化的研究过程中,发现芳基次膦酰胺化合物可以高效地转化为芳基次膦酸酯和芳基膦化氢,收率分别为98%和82%。因此,本文报道的实验结果可以为多芳基膦化合物的合成提供一个新的方法。The C-H arylation of various phosphinic acid derivatives was investigated. After a comprehensive screen of various reaction parameters, we found that direct C--H arylation of aryl phosphinamides could proceed effectively with Pd （OAc）2 as catalyst, Ag/CO3 as oxidant, and benzoquinone （BQ） as additive in DMF. Mechanistic study revealed that the reaction proceeded via a Pd（ Ⅱ） to Pd（0） cycle. Further elaboration demonstrated that arylated phosphinamides could be converted into the corresponding aryl phosphinates and H-biaryl phosphines in high efficiency, with yields of 98% and 82%, respectively. Consequently, the results presented herein would offer a new method for the synthesis of polyaryl phosphorus compounds.

关 键 词：钯 C—H键官能化 次膦酰胺 芳基化 衍生化 

分 类 号：O621.2[理学—有机化学]