Development of P- and N-Chirogenic Ligands Based on Chiral Induction from a Phosphorus Donor to a Nitrogen Donor in Palladium Complexes
作者:Takahiro Iwamoto、Yoshiyuki Mizuhata、Norihiro Tokitoh、Masaharu Nakamura
DOI:10.1021/acs.organomet.0c00154
日期:2020.5.26
backbone, as a novel class of chiral ligands possessing chirogenic donors. Ligand 1a (R = Me) stereoselectively coordinated with PdCl2 to predominantly afford the P- and N-chirogenic metal complex 4a having an RN,SP configuration. In contrast, ligands 1b (R = iPr) and 1c (R = tBu) produced a mixture of diastereomers derived from two possible N-centered configurations. In complex 4a, the N-centered configuration
我们在本文中设计并合成了氨基膦配体1a – c,其在吡啶撑骨架上带有一个P色性基团(R)-P t BuMe和一个N基团(NHR),作为一类具有新颖性的手性配体生色的供体。配体1a(R = Me)与PdCl 2立体选择性配位,主要提供具有R N,S P构型的P-和N-手性金属配合物4a。相反,配体1b(R = i Pr)和1c(R = tBu)产生了源自两种可能的以N为中心的构型的非对映异构体的混合物。在复合物4a中,通过P- t Bu和N-Me之间的贯穿空间吸引相互作用,P致色中心有效地控制了N中心构型。埋藏体积分析表明,该新型配体产生了源自空间和电子不对称性的独特的C 1对称手性环境。