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Diastereoselective Synthesis of P‐Chirogenic and Atropisomeric 2,2′‐Bisphosphino‐1,1′‐binaphthyls Enabled by Internal Phosphine Oxide Directing Groups
Author(s) -
Xue Qingquan,
Huo Shangfei,
Wang Tingyi,
Wang Zeming,
Li Jianli,
Zhu Meifang,
Zuo Weiwei
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202001561
Subject(s) - stereocenter , chirality (physics) , phosphine oxide , chemistry , phosphine , axial chirality , nucleophile , reagent , medicinal chemistry , oxide , enantioselective synthesis , stereoselectivity , ketone , stereochemistry , organic chemistry , catalysis , quantum mechanics , quark , nambu–jona lasinio model , chiral symmetry breaking , physics
Diphosphine ligands that merge both axial and P‐centered chirality may exhibit superior or unique properties. Herein we report the diastereoselective introduction of P‐centered chirality at the 2‐position of the axially chiral 2′‐(phosphine oxide)‐1,1′‐binaphthyl scaffold. A lithium–bromide exchange reaction of a 2‐bromo‐2′‐(phosphine oxide)‐1,1′‐binaphthyl and treatment with dichlorophosphines followed by a nucleophilic organometallic reagent afforded unsymmetrical 2‐phosphino‐2′‐(phosphine oxide)‐1,1′‐binaphthyls with binaphthyl axial chirality and one or two phosphorus stereocenters with a variety of P substituents. The final diastereomerically pure 2,2′‐bisphosphino‐1,1′‐binaphthyls were obtained by reduction of the phosphine oxide directing group. Preliminary results demonstrated that a ligand with this hybrid chirality could induce higher stereoselectivity in the metal‐complex‐catalyzed asymmetric hydrogenation of a dialkyl ketone.