Nemoto Tetsuhiro, Matsumoto Takayoshi, Masuda Takamasa, Hitomi Tsukasa, Hatano Keiichiro, Hamada Yasumasa
Graduate School of Pharmaceutical Sciences, Chiba University, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.
J Am Chem Soc. 2004 Mar 31;126(12):3690-1. doi: 10.1021/ja031792a.
We successfully synthesized a novel P-chirogenic diaminophosphine oxide 4, which was applied to catalytic enantioselective construction of quaternary carbon centers using Pd-catalyzed asymmetric allylic substitution with various beta-keto esters (up to 99% yield, 94% ee). Preliminary mechanistic studies indicated that two molecules of 8 coordinate to the Pd metal in a monodentate fashion, resulting in the formation of Pd complex 9 (Pd:8 = 1:2), which functions as the active species.
我们成功合成了一种新型的P-手性二氨基氧化膦4，并将其应用于钯催化的与各种β-酮酯的不对称烯丙基取代反应中，用于催化对映选择性构建季碳中心（产率高达99%，对映体过量值高达94%）。初步机理研究表明，两个8配位的分子8以单齿方式与钯金属配位，从而形成钯配合物9（钯:8 = 1:2），该配合物作为活性物种发挥作用。
