Chiral Electron-Rich PNP Ligand with a Phospholane Motif: Structural Features and Application in Asymmetric Hydrogenation

Wang, Heng1,2,3; Zhang, Yao1,2; Yang, Tilong1,2; Guo, Xiaochong1,2; Gong, Quan1,2; Wen, Jialin1,2,4; Zhang, Xumu1,2

2020-11-20

10.1021/acs.orglett.0c03159

ORGANIC LETTERS   影响因子和分区

1523-7060

1523-7052

Despite the remarkable reactivity that was achieved by a series of transition-metal catalysts with a PNP type ligand, the electron-rich chiral PNP ligands have still been rarely reported because of the difficulties in synthesis and the nature of air-sensitivity. Herein, we report a novel chiral PNP ligand (Heng-PNP) with both a rigid backbone and a bulky tert-butyl group on the phospholane motif. We successfully obtained its divalent iron complex. The chiral environment of its Ir(III) complex was also discussed with quadrant analysis. This tridentate ligand was applied in iridium-catalyzed asymmetric hydrogenation of challenging diaryl ketones: up to 98% ee and 500 TON are achieved. Computational study showed that the twist of conjugate aryl group in the substrate (induced by the special chiral pocket of Ir/Heng-PNP complex) leads to the energy difference in the enantiodetermining step.

SCI ; IC

英语

NI论文

第一 ; 通讯

National Natural Science Foundation of China[21801118]

Chemistry

Chemistry, Organic

WOS:000592988800010

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Temple Univ, Dept Chem, Philadelphia, PA 19122 USA
4.Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Shenzhen 518055, Peoples R China

Wang, Heng,Zhang, Yao,Yang, Tilong,et al. Chiral Electron-Rich PNP Ligand with a Phospholane Motif: Structural Features and Application in Asymmetric Hydrogenation[J]. ORGANIC LETTERS,2020,22(22).

Wang, Heng.,Zhang, Yao.,Yang, Tilong.,Guo, Xiaochong.,Gong, Quan.,...&Zhang, Xumu.(2020).Chiral Electron-Rich PNP Ligand with a Phospholane Motif: Structural Features and Application in Asymmetric Hydrogenation.ORGANIC LETTERS,22(22).

Wang, Heng,et al."Chiral Electron-Rich PNP Ligand with a Phospholane Motif: Structural Features and Application in Asymmetric Hydrogenation".ORGANIC LETTERS 22.22(2020).