Catalysis Letters ( IF 2.3 ) Pub Date : 2021-05-07 , DOI: 10.1007/s10562-021-03643-3 Simon Doherty , Julian G. Knight , Tina S. T. Tran , Hussam Y. Alharbi , Daniel O. Perry
Abstract
The iridium-catalyzed C-H borylation of diethyl phenylphosphonate results in nonselective mono and bisborylation to afford a near statistical mixture of 3-, 3,5- and 4-boryl substituted aryl phosphonates whereas 3-substituted aryl phosphonates undergo highly regioselective C-H borylation to afford the corresponding meta-phosphonate substituted arylboronic esters as the sole product; the resulting boronic esters were used as nucleophilic reagents in a subsequent palladium-catalyzed Suzuki–Miyaura cross-coupling to generate a range of biarylmonophosphonates. Gratifyingly, the Suzuki–Miyaura cross-coupling can be conducted without purifying the boronic ester which greatly simplifies the synthetic procedure.
Graphical Abstract
中文翻译:
钯催化的膦酸酯化,铱催化的CH硼酸酯化反应,钯催化的Suzuki-Miyaura交叉偶联合成联芳基单膦酸酯
摘要
铱催化的苯基膦酸二乙酯的CH硼化反应会导致非选择性的单和双硼化反应,从而提供3-,3,5-和4-硼基取代的芳基膦酸酯的近统计混合物,而3-取代的芳基膦酸酯会进行高度区域选择性的CH硼酸酯化,从而得到单独的产物是相应的间膦酸酯取代的芳基硼酸酯;所得的硼酸酯在随后的钯催化的Suzuki-Miyaura交叉偶联中用作亲核试剂,以生成一系列联芳基单膦酸酯。令人欣慰的是,无需纯化硼酸酯即可进行铃木-宫浦交叉偶联,大大简化了合成过程。