A comparative study of the copolymerization of racemic propylene oxide (PO) with CO2 catalyzed by racemic (salcy)CoX (salcy = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane; X = perfluorobenzoate (OBzF5) or 2,4-dinitrophenoxy (DNP)) in the presence of a [PPN]Cl ([PPN] = bis(triphenylphosphine)iminium) cocatalyst is performed in bulk at 21 °C and a 2.5 MPa pressure of CO2. The increase in the nucleophilicity of an attacking anion results in the increase in the copolymerization rate. Racemic (salcy)CoX provides a high selectivity of the copolymerization, which can be higher than 99%, and the living polymerization mechanism. Poly(propylene carbonate) (PPC) with bimodal molecular weight distribution (MWD) is formed throughout copolymerization. Both modes are living and are characterized by low dispersity, while their contribution to MWD depends on the nature of the attacking anion. The racemic (salcy)CoDNP/[PPN]DNP system is found to be preferable for the production of PPC with a high yield and selectivity.
To evaluate the differences in action of commercially available 2-oxoglutarate mimetics and “branched-tail” oxyquinoline inhibitors of hypoxia-inducible factor prolyl hydroxylase (HIF PHD), the inhibitors’ IC50 values in the activation of HIF1 ODD-luciferase reporter were selected for comparative transcriptomics. Structure–activity relationship and computer modeling for the oxyquinoline series of inhibitors led to the identification of novel inhibitors, which were an order of magnitude more active in the reporter assay than roxadustat and vadadustat. Unexpectedly, 2-methyl-substitution in the oxyquinoline core of the best HIF PHD inhibitor was found to be active in the reporter assay and almost equally effective in the pretreatment paradigm of the oxygen-glucose deprivation in vitro model. Comparative transcriptomic analysis of the signaling pathways induced by HIF PHD inhibitors showed high potency of the two novel oxyquinoline inhibitors (#4896-3249 and #5704-0720) at 2 μM concentrations matching the effect of 30 μM roxadustat and 500 μM dimethyl oxalyl glycine in inducing HIF1 and HIF2-linked pathways. The two oxyquinoline inhibitors exerted the same activation of HIF-triggered glycolytic pathways but opposite effects on signaling pathways linked to alternative substrates of HIF PHD 1 and 3, such as p53, NF-κB, and ATF4. This finding can be interpreted as the specificity of the 2-methyl-substitute variant for HIF PHD2.
A series of novel functional polycarbonates, specifically poly(solketal glycidyl ether carbonate-co-propylene carbonate)s with varying compositions, were synthesized through the ring-opening copolymerization of solketal glycidyl ether, propylene oxide, and carbon dioxide. The reaction was catalyzed by rac-(salcy)CoIIIX complexes with bis(triphenylphosphine)iminium salts as co-catalysts, achieving high selectivity. The resulting terpolymers exhibited number-average molecular weights ranging from 2 × 104 to 1 × 105 and a narrow, bimodal molecular weight distribution, with dispersities of 1.02–1.07 for each mode. Interestingly, the addition of a small amount of water to the reaction mixture yielded a terpolymer with a unimodal molecular weight distribution and a dispersity of 1.11. Subsequent acidic hydrolysis of the solketal protective groups produced poly(glyceryl glycerol carbonate-co-propylene carbonate). All terpolymers were amorphous, with Tg near or below room temperature. The hydroxyl-functional polycarbonates underwent cyclodepolymerization under milder conditions compared to polycarbonates with protected hydroxyl groups.
1 August 2026 in Russian Journal of Organic Chemistry
The synthesis of imidazo[1,2-a]pyridines was carried out via 5-exo-dig cyclization of the corresponding N-(pyridin-2-yl)methanimines and terminal acetylenes, catalyzed by the cationic complex [Cu(CH3CN)4]BF4. For the first time, the catalytic activity of the cationic Cu(I) complex in the synthesis of imidazo[1,2-a]pyridine derivatives was investigated. A series of 15 derivatives of imidazo[1,2-a]pyridine with various substituents (Cl, Br, CO2Et, and OMe) was obtained with yields of 52–69%.