Efficient Synthesis of Pharmaceutical Intermediates from Biomass-Derived Aldehydes and Ketones over Robust Ni_xAl Nanocatalysts

Abstract

Heterogeneous catalytic reductive amination of biomass-based carbonyl compounds is a highly attractive strategy to realize green and sustainable amine synthesis under mild conditions. Herein, N 1,N 1-diethyl-1,4-pentanediamine, a key side chain of chloroquine pharmaceuticals, was highly selectively synthesized through the reductive amination of 5-diethylamino-2-pentanone on active Ni x Al nanocatalysts with different Ni/Al molar ratios prepared by the simple co-precipitation method. The Ni1Al catalyst presented the highest target diamine product yield (up to 99%) among the Ni x Al catalysts. This catalyst also exhibited remarkable stability in a fixed-bed reactor without deactivation after 200 h of continuous operation, thanks to its good anti-sintering and anti-oxidation properties. Systematic structure characterizations and catalytic activity tests showed that their catalytic activity depended sensitively on the Ni/Al molar ratio, which governed the dispersion, reducibility, and surface acidity of the catalysts. The synergic catalysis of highly dispersed active Ni0 nanoparticles with abundant adjacent surface Lewis acidic sites accounted for the outstanding catalytic performance of the Ni1Al catalyst. Moreover, such novel catalysts also presented high activity in the reductive amination of several other biomass-derived aldehydes and ketones to produce the corresponding amines, achieving 91–99% yields under mild conditions of 80–100 °C and 1–2 MPa.

Ionic polyamide boosting Ru efficiency in reductive amination of carbonyl compounds

“…In general, due to the high reactivity of the aldehyde group, some unwanted side products are often generated and selective preparation of the corresponding primary amines is more challengeable. 58,59 In spite of these issues, 3%Ru@iTP was proved to be a highly efficient and selective reductive amination catalyst for the production of primary amines from aldehydes, showing good to high yields (up to 99%) (Table 3). Simple linear as well as annular aliphatic aldehydes could afford primary amine yields from 83% to 99% (16)(17)(18)(19).…”

Exemplifying Natural (R)-β-Transamination Potential of Fold Type-IV Transaminase for Kinetic Resolution of rac-β-Amino Acids Synthesized from Aldehydes

“…Aldehydes derived from biomass, such as furfural, 5-hydroxymethylfurfural, vanillin, and its analogs, are plentiful and renewable. By catalytic upgrading, they have been widely used to produce valuable chemicals, biofuels, and renewable materials …”

Synthesis of a renewable bisguaiacol amide and its hydrogen bonding effect on enhancing polybenzoxazine performance

“…23 A family of vanillin derivatives, including vanillic acid, vanillyl alcohol and vanillyl amine, can be simply obtained from vanillin with high yields. 24,25 To incorporate two phenol groups into one molecule, several strategies involving vanillin derivatives have been reported. The successful routes include the synthesis of bisguaicol F from guaiacol and vanillin 26 and the preparation of spiro-bisphenol via a condensation reaction of vanillin and pentaerythritol aldol.…”