Facile Aminolysis Research Articles

Facile Synthesis of Multifunctional Bioreducible Polymers for mRNA Delivery.

Bioreducible polymeric mRNA carriers are an emerging family of vectors for gene delivery and vaccine development. A few bioreducible systems have been generated through aqueous-phase ring-opening polymerization of lipoic acid derivatives, however this methodology limits hydrophobic group incorporation and functionality into resulting polymers. Herein, a poly(active ester)disulfide polymer is synthesized that can undergo facile aminolysis with amine-containing substrates under stoichiometric control and mild reaction conditions to yield a library of multifunctional polydisulfide polymers. Functionalized polydisulfide polymer species form stable mRNA-polymer nanoparticles for intracellular delivery of mRNAs in vitro. Alkyl-functionalized polydisulfide-RNA nanoparticles demonstrate rapid cellular uptake and excellent biodegradability when delivering EGFP and OVA mRNAs to cells in vitro. This streamlined polydisulfide synthesis provides a new facile methodology for accessing multifunctional bioreducible polymers as biomaterials for RNA delivery and other applications.

Production of Piperidine and δ‐Lactam Chemicals from Biomass‐Derived Triacetic Acid Lactone

AbstractPiperidine and δ‐Lactam chemicals have wide application, which are currently produced from fossil resource in industry. Production of this kind of chemicals from lignocellulosic biomass is of great importance, but is challenging and the reported routes give low yield. Herein, we demonstrate the strategy to synthesize 2‐methyl piperidine (MP) and 6‐methylpiperidin‐2‐one (MPO) from biomass‐derived triacetic acid lactone (TAL) that is produced microbially from glucose. In this route, TAL was firstly converted into 4‐hydroxy‐6‐methylpyridin‐2(1H)‐one (HMPO) through facile aminolysis, subsequently HMPO was selectively transformed into MP or MPO over Ru catalysts supported on beta zeolite (Ru/BEA‐X, X is the molar ratio of Si to Al) via the tandem reaction. It was found that the yield of MP could reach 76.5 % over Ru/BEA‐60 in t‐BuOH, and the yield of MPO could be 78.5 % in dioxane. Systematic studies reveal that the excellent catalytic performance of Ru/BEA‐60 was closely correlated with the cooperative effects between active metal and acidic zeolite with large pore geometries. The related reaction pathway was studied on the basis of control experiments.

Production of Piperidine and δ-Lactam Chemicals from Biomass-Derived Triacetic Acid Lactone.

Piperidine and δ-Lactam chemicals have wide application, which are currently produced from fossil resource in industry. Production of this kind of chemicals from lignocellulosic biomass is of great importance, but is challenging and the reported routes give low yield. Herein, we demonstrate the strategy to synthesize 2-methyl piperidine (MP) and 6-methylpiperidin-2-one (MPO) from biomass-derived triacetic acid lactone (TAL) that is produced microbially from glucose. In this route, TAL was firstly converted into 4-hydroxy-6-methylpyridin-2(1H)-one (HMPO) through facile aminolysis, subsequently HMPO was selectively transformed into MP or MPO over Ru catalysts supported on beta zeolite (Ru/BEA-X, X is the molar ratio of Si to Al) via the tandem reaction. It was found that the yield of MP could reach 76.5 % over Ru/BEA-60 in t-BuOH, and the yield of MPO could be 78.5 % in dioxane. Systematic studies reveal that the excellent catalytic performance of Ru/BEA-60 was closely correlated with the cooperative effects between active metal and acidic zeolite with large pore geometries. The related reaction pathway was studied on the basis of control experiments.

Aminolysis of polyethylene terephthalate fabric by a method involving the gradual concentration of dilute ethylenediamine

Aminolysis of polyethylene terephthalate (PET) fibers can endow fibers high hydrophilicity and reactive NH2 groups; however, the ethylenediamine solution aminolysis method severely damages the PET fibers. In this paper, a facile aminolysis method involving the gradual concentration of dilute ethylenediamine was developed to aminate PET fibers. The results showed that the hydrophilicity of the PET fabric substantially improved and that reactive NH2 groups were introduced onto the PET fibers. The water absorption time and contact angle of the treated PET fabrics decreased to 15s and 0°, respectively. The liquid wicking height of the treated PET fabric increased from 0.4cm (original PET fabric) to 11.0cm. Fourier transform infrared spectra demonstrated that NH2 groups were successfully introduced onto the PET fibers. Scanning electron microscopy showed almost no difference between the surfaces of the original and treated PET fibers. X-ray diffraction analysis indicated that the main structure of the PET fibers was well maintained. The aminated PET fabrics retained the weight loss, breaking strength and elongation, crease recovery angle, stiffness and whiteness of the original PET fabrics. The aminolysis of PET fibers via the gradual concentration of dilute ethylenediamine is a promising method for the efficient, rapid, and eco-friendly modification of PET fibers.

Glycogen phosphorylase inhibitory effects of 2-oxo-1,2-dihydropyridin-3-yl amide derivatives

Glycogen phosphorylase (GP) plays a crucial role in the conversion of glycogen to glucose-1-phosphate (and in turn glucose) and is a promising target for therapeutic intervention in diabetes. In this study we synthesized new derivatives of 2-oxo-1,2-dihydropyridin-3-yl amides using a facile aminolysis reaction, in which different alkyl and aryl esters and amides are substituted at N-1 and C-3 of the heterocyclic ring. The in vitro inhibitory activity of compounds against glycogen phosphorylase was evaluated. From this series the most potent compound exhibits good GPa inhibition (IC 50 = 6.3 μM). A preliminary study of these compounds showed that anti-GP activity was decreased by the incorporation of a C3–N carbonyl group and favored by increased lipophilicity.

ChemInform Abstract: Facile Aminolysis of Alkyl 2‐Arylsulfinylacetates at High Pressure.

ChemInform Abstract: Facile Aminolysis of Alkyl 2‐Arylsulfinylacetates at High Pressure.

Selective Aminolysis of Benzoates and Acetates of α-Hydroxy Acids and Phenols With Benzylamine and Butan-1-amine

Benzoates and acetates of a-hydroxy acids and phenols undergo facile aminolysis on treating with benzylamine or butan-1-amine in benzene at room temperature. Under the same conditions acetates and benzoates of alcohols are unaffected.

Unusually facile aminolysis of β-ketoesters

The unusually facile aminolysis of β-ketoesters does not proceed via simple amine nucleophilic attack on the ester carbonyl.

Facile aminolysis of epoxides with diethylaluminum amides

Treatment of an epoxide with a diethylaluminum amide in dichloromethane at room temperature affords the corresponding β-amino alcohol in good yield.