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Synthesis of Chiral Polyamides Containing an ( R , R )‐1,2‐Diphenylethylenediamine Monosulfonamide Structure and Their Application to Asymmetric Transfer Hydrogenation Catalysis
Author(s) -
Itsuno Shinichi,
Takahashi Shotaro
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201601220
Subject(s) - polyamide , catalysis , chiral ligand , chemistry , sulfonamide , ligand (biochemistry) , polymer chemistry , condensation polymer , transfer hydrogenation , polymer , metal , enantioselective synthesis , organic chemistry , ruthenium , biochemistry , receptor
A chiral main‐chain polyamide containing an ( R , R )‐1,2‐diphenylethylenediamine monotoluenesulfonamide (TsDPEN) repeating unit was prepared. Polycondensation of dicarboxylic acid dichloride with the chiral bisaniline of N ‐ tert ‐butoxycarbonyl‐protected TsDPEN was successful and afforded a chiral polyamide with a TsDPEN repeating unit as the chiral ligand structure. Treatment of the main‐chain polymer chiral ligand with transition‐metal complexes, such as [IrCl 2 Cp*] 2 (Cp*=η 5 ‐pentamethylcyclopentadienyl), [RhCl 2 Cp*] 2 , and [RuCl 2 ( p ‐cymene)] 2 , afforded polymer chiral metal complexes. Asymmetric transfer hydrogenation of a cyclic sulfonamide was efficiently catalyzed by the chiral TsDPEN polymer–metal complex to give an optically active cyclic sulfonylamine with quantitative conversion and high enantioselectivity. The polymer catalyst was easily recovered from the reaction mixture and reused several times without any loss in catalytic activity or enantioselectivity.