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 s...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.展开更多
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 ...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.展开更多
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]-...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.展开更多
基金the financial support by the National Natural Science Foundation of China(No.20373014).
文摘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.
基金supported by the National Natural Science Foundation of China(Grant Nos.20225204,20121202,20l320l0 and 20372071)the Chinese Academy of Sciences.the Maior Basic Research Development Program of China(Grant No.G2000077506)the Science and Technology Commission of Shang-hai M unicipality
文摘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.
基金the National Natural Science Foundation of China(grant nos.21871268 and 22071250)the Natural Science Foundation of Guangdong Province of China(grant no.2020A1515011428)the“BAGUI Scholar”Program of Guangxi Province of China,and the SKLRD Project(grant no.SKLRD-Z-202014)for financial support.
文摘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.
