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One‐Step Synthesis of Chiral Azamacrocycles via Palladium‐Catalyzed Enantioselective Amination of 1,5‐Dichloroanthraquinone and 1,5‐Dichloroanthracene
Author(s) -
Ranyuk Elena R.,
Averin Alexei D.,
Beletskaya Irina P.
Publication year - 2010
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.201000181
Subject(s) - chemistry , enantioselective synthesis , palladium , amination , phosphine , enantiomer , enantiomeric excess , crystallization , catalysis , combinatorial chemistry , organic chemistry
Asymmetric amination of 1,5‐dichloroanthraquinone and 1,5‐dichloroanthracene with di‐ and trioxadiamines catalyzed by palladium complexes with various chiral phosphine ligands gave chiral macrocycles with ee values of up to 60%. The dependence of the chemical yields and enantiomeric excess on the nature of the starting compounds and the phosphine ligands employed was demonstrated. An unexpected spontaneous resolution upon crystallization of the macrocycle comprising anthraquinone and dioxadiamine moieties was observed while in the case of the macrocycle with a trioxadiamine linker racemic monocrystals were obtained. Crystallization of the enantiomerically enriched mixtures afforded chiral macrocycles with 88–99% ee .