Synthesis of a Bolm's 2,2 '-Bipyridine Ligand Analogue and Its Applications

0492366 - ÚOCHB 2019 RIV DE eng J - Journal Article
Bednářová, E. - Dračínský, Martin - Malatinec, Š. - Císařová, I. - Lamaty, F. - Kotora, M.
Synthesis of a Bolm's 2,2 '-Bipyridine Ligand Analogue and Its Applications.
Advanced Synthesis & Catalysis. Roč. 360, č. 15 (2018), s. 2869-2878. ISSN 1615-4150. E-ISSN 1615-4169
R&D Projects: GA MŠMT(CZ) LO1304
Institutional support: RVO:61388963
Keywords : catalysis * enantioselective synthesis * cyclotrimerization * bipyridines * chiral ligands
OECD category: Organic chemistry
Impact factor: 5.451, year: 2018

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, 99/1dr, 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.
Permanent Link: http://hdl.handle.net/11104/0285923