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Enantiodivergent Kinetic Resolution of 1,1′‐Biaryl‐2,2′‐Diols and Amino Alcohols by Dipeptide‐Phosphonium Salt Catalysis Inspired by the Atherton–Todd Reaction
Author(s) -
Fang Siqiang,
Tan JianPing,
Pan Jianke,
Zhang Hongkui,
Chen Yuan,
Ren Xiaoyu,
Wang Tianli
Publication year - 2021
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.202102352
Subject(s) - phosphonium , chemistry , kinetic resolution , bifunctional , phosphonium salt , dipeptide , catalysis , enantiomer , enantioselective synthesis , combinatorial chemistry , pyridinium , selectivity , organocatalysis , organic chemistry , peptide , biochemistry
A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide‐phosphonium salt‐catalyzed Atherton–Todd (A‐T) reaction. This flexible approach led to both R ‐ and S ‐enantiomers by fine‐tuning of bifunctional phosphonium with excellent selectivity factors ( s ) of up to 1057 and 525, respectively. The potential of newly synthesized O‐phosphorylated biaryl diols was illustrated by the synthesis of axially chiral organophosphorus compounds. Mechanistic investigations suggest that the bifunctional phosphonium halide catalyst differentiates between the in‐situ‐generated P‐species in the A‐T process, mainly involving phosphoryl chloride and phosphoric anhydride, thus leading to highly enantiodivergent O‐phosphorylation reactions. Furthermore hydrogen bonding interactions between the catalysts and phosphorus molecules were crucial in asymmetric induction.