Phosphorus Ligands from the Zhang Lab:Design,Asymmetric Hydrogenation,and Industrial Applications

Chiral phosphorus ligands have played a crucial role for the recent advances in asymmetric catalysis.This review summarizes chiral phosphorus ligands developed from the Laboratory of Professor Xumu Zhang in the latest 25 years.A number of iconic phosphorus ligands including bisphosphorus ligands with rigid chiral backbone such as BICP,PennPhos,TunePhos,and f-Binaphane,P-chiral bisphosphorus ligands TangPhos,Binapine,and DuanPhos,phosphine-phosphoramidte ligand YanPhos,noncovalent interaction-assisted ferrocenyl phosphorus ligand ZhaoPhos and WudaPhos,and tridentate ferrocenyl phosphorus ligands f-amphox are introduced,and their applications in asymmetric hydrogenation are emphasized.

Recent advances in catalytic asymmetric hydrogenation:Renaissance of the monodentate phosphorus ligands

The history for the development of chiral phos- phorus ligands in catalytic asymmetric hydrogenation is briefly highlighted. This review focuses on the recent ad- vances in the synthesis of the monodentate phosphorus ligands and their applications in catalytic asymmetric hydrogenation. The examples highlighted in this article clearly demonstrated the importance and advantages of monodentate phosphorus ligands, which had been ignored for 30 a and experienced arenaissance at the very beginning of this millennium, particularly in the area of asymmetric hydrogenation.

Spacial Structure of Cationic Phosphorus Ligand-Ru （Ⅱ） Halide Complexes-by DFT Study

The full-parameter geometry optimization of cationic （ S ） - BINAP - Ru （ Ⅱ ） halide complex was performed by DFT method using B3LYP, PW91 and PBE potentials with several basis sets. PW91 with 3-21G / SDD basis sets is found to be the most suitable method with consideration of both precision and efficiency. The dihedral angles （ θ ） of the binaphthyl or biphenyl with different phosphorus ligand - Ru （ Ⅱ ） halide complexes were found changing from 59.9 to 79.3 degree, while the natural bite angle （ βn ） of those complexes only changes from 87.4 to 90.3 degree. It is different from the common view of asymmetric organic chemists＇ that θ directly influences βn.

Inherently Chiral 6,7-Diphenyldibenzo [e,g][1,4]diazocine: Enantioselective Synthesis and Application as a Ligand Platform

Inherently chiral 6,7-diphenyldibenzo[e,g][1,4]diazocine(DDD)has been synthesized enantioselectively for the first time via chiral phosphoric acid(CPA)-catalyzed cyclocondensation of readily available[1,1′-biphenyl]-2,2′-diamine(1a)and benzil(2a)in 82%yield,with 98%ee under mild reaction conditions.The strategy could also be applied to racemic biaryl diamines through kinetic resolution.The unexpectedly high interconversion energy barriers between the enantiomers(ΔG=39.5 kcal/mol)and the chemical stability rendered DDD an ideal platform for developing new chiral ligands and catalysts.Unique inherently chiralDDD-based phosphoramidites,phosphoric acid,mono-and diphosphine ligands were prepared from optically pure diphenol derivative DDDOL as a common precursor.Preliminary asymmetric reactions catalyzed by Pd or Rh in the presence of newly developed ligands exhibited comparable or even better enantioselectivities than the corresponding BINOLor SPINOL-derived ligands.Density functional theory calculation revealed the origin of the enantioselectivity during the process.

Biosorption and retention of orthophosphate onto Ca(OH)_2-pretreated biomass of Phragmites sp.

The biosorption of phosphorus in the form of orthophosphate（Po） from wastewater using biomass as the sorbent is of potential importance because the Po-loaded biomass could be applied in the agricultural sector as fertilizer and soil conditioner. However, biomass generally displays a very low affinity for Posorption and therefore biomass surface modification is required. In the present study, the biomass（as model grinded leaves of Phragmites sp. were used）was pretreated with Ca（OH）2to enhance Pobiosorption capacity（qe）. The results indicate that the alkaline pretreatment resulted in a modification of surface functional groups. It was concluded that the main sorption mechanisms were ligand exchange and electrostatic attraction. A series of experiments were conducted to investigate the performance of the pretreated biomass for Pouptake under various conditions. Isotherm and thermodynamic studies were also applied and analyzed. The biosorption process was best described by the pseudo-second order kinetic model and Langmuir isotherm, which gave a qmaxof 12.27 mg P/g at 25°C and p H 7. The Ca（OH）2treated Phragmites biomass applied in this study for Porecovery may present some potential advantages in terms of costs and environmental impact.