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Synthesis of a Bolm's 2,2′‐Bipyridine Ligand Analogue and Its Applications
Author(s) -
Bednářová Eva,
Dračínský Martin,
Malatinec Štefan,
Císařová Ivana,
Lamaty Frédéric,
Kotora Martin
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.201800452
Subject(s) - chemistry , aldol reaction , ligand (biochemistry) , epoxide , enantioselective synthesis , bipyridine , reagent , yield (engineering) , catalysis , chiral ligand , combinatorial chemistry , stereochemistry , medicinal chemistry , organic chemistry , biochemistry , materials science , receptor , crystal structure , metallurgy
A new method of synthesis of an analogue of Bolm's 2,2′‐bipyridine ligand based on the catalytic [2+2+2] cyclotrimerization of 1‐halodiynes with nitriles was developed. Crucial step of the whole synthesis turned out to be homodimerization of a substituted 2‐bromopyridine to the corresponding bipyridine, that was studied and optimized. The newly prepared bipyridine ( S,S )‐ 2 was then tested as a chiral ligand in metal‐catalyzed enantioselective reactions. Out of the studied reactions the most promising results were obtained in epoxide ring opening (82% yield, 98% ee) and Mukaiyama aldol reaction (>96% yield, 99/1 dr, 92% ee). In the case of Mukaiyama‐aldol reaction as well as in the Michael addition, novel ligand 2 proved its robustness compared to Bolm's ligand as it was less sensitive to the purity of used reagents.