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An Atropos Chiral Biphenyl Bisphosphine Ligand Bearing Only 2,2′‐Substituents and Its Application in Rh‐Catalyzed Asymmetric Hydrogenation
Author(s) -
Jia Jia,
Ling Zheng,
Zhang Zhenfeng,
Tamura Ken,
Gridnev Ilya D.,
Imamoto Tsuneo,
Zhang Wanbin
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201701281
Subject(s) - chemistry , diastereomer , ligand (biochemistry) , biphenyl , reactivity (psychology) , catalysis , stereochemistry , asymmetric hydrogenation , enantioselective synthesis , chiral ligand , medicinal chemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
Abstract An atropos chiral biphenyl bisphosphine ligand bearing only 2,2′‐substituents was rationally designed and easily synthesized utilizing a bulky chiral t ‐butylmethylphosphino block. Computational results showed a large difference in the free energies between the two diastereomers (7.8 kcal/mol) and attainable rotational energy barriers from one diastereomer to another (27.7 kcal/mol and reverse 19.9 kcal/mol). This ligand avoids the time‐consuming optical resolution generally needed for the preparation of axially chiral ligands and shows high reactivity and enantioselectivity in Rh‐catalyzed asymmetric hydrogenations.