Development of P- and N-Chirogenic Ligands Based on Chiral Induction from a Phosphorus Donor to a Nitrogen Donor in Palladium Complexes
Development of P- and N-Chirogenic Ligands Based on Chiral Induction from a Phosphorus Donor to a Nitrogen Donor in Palladium Complexes
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DOI：
10.1021/acs.organomet.0c00154
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发表时间：
2020-05-26
期刊：
影响因子：
2.8
通讯作者：
Nakamura, Masaharu
中科院分区：
文献类型：
--
作者：
Iwamoto, Takahiro;Mizuhata, Yoshiyuki;Nakamura, Masaharu
本论文设计并合成了一类新型的手性给体手性配体--氨基膦配体1a-c，它们在吡啶主链上带有P-手性基团(R)-PtBuMe和N-基团(NHR)。配体1a(R=Me)与PdCl2立体选择性配位，得到具有R-N、S-P构型的P-和N-手性金属配合物4a。相反，配体1b(R=IPR)和1c(R=TBU)产生了来自两种可能的N中心构型的非对映异构体的混合物。在复合体4a中，通过P-TBU和N-Me之间的空间吸引相互作用，N中心构型被生核中心有效地控制。掩埋体积分析表明，这种新的配体创造了一个独特的C-1对称的手性环境，源于空间和电子不对称。
We herein designed and synthesized amino-phosphine ligands 1a-c, which bear a P-chirogenic group, (R)-PtBuMe, and an N-group (NHR) on the pyridylene 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 R-N,S-P 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 was efficiently controlled by the Pchirogenic center via through-space attractive interactions between P-tBu and N-Me. Buried volume analysis indicated that this novel ligand creates a unique C-1-symmetric chiral environment derived from both steric and electronic asymmetry.