Catalytic transformations of glycerol via hydroxyacetone into nitrogen heterocycles of industrial interest DOI Creative Commons

Jaime Mazarío Santa-Pau

Published: Dec. 15, 2021

Based around the idea of searching for sustainable alternatives to fossil sources manufacturing fuels and chemical products, this doctoral thesis addresses development new catalytic processes centered on glycerol valorization, which is main by-product biodiesel synthesis.In sense, aim focused using it as a carbon source generate nitrogen heterocycles industrial interest, specifically, produce 2methylpiperazine 2-methylpyrazine.However, due low reactivity severe reaction conditions necessary carry out transformations towards these N-heterocycles, previous detailed research optimize understand selective dehydration process hydroxyacetone (or acetol) was undertaken.Through obtaining intermediate compound, has been possible develop efficient production under reasonably moderate conditions.In regard, Cu-Mg-Al hydrotalcite precursors give rise family materials based mixed oxides capable, if their composition adequately optimized, carrying acetol continuously with yields ≈40%.In addition, catalysts are stable more than 8 hours operational conditions, showing excellent regeneration capacity reusability.In same way, through combination characterization studies, interesting mix acid-base redox centers exhibited by allowed advancing significantly in state art regarding understanding reaction.Hence, verify fundamental role Cu species and, Cu(I) present catalysts, generation glyceraldehyde critical production.Similarly, acid catalyst facilitate first adsorption glycerol, thus accelerating reaction.However, need achieve higher productivities from stand chance succeed overall strategy motivated study second copper oxide supported different metal (SiO2, Al2O3 ZrO2) combining Lewis high exposure.The proper selection optimization lead reaching, several them, 60% much concentrations starting feed.

Language: Английский

Organocatalytic valorisation of glycerol via a dual NHC-catalysed telescoped reaction DOI Creative Commons
Anton Axelsson,

Amandine Antoine-Michard,

Henrik Sundén

et al.

Green Chemistry, Journal Year: 2017, Volume and Issue: 19(11), P. 2477 - 2481

Published: Jan. 1, 2017

NHC-catalysis enables the successful functionalisation of glycerol through a telescoped reaction strategy involving carbonation and subsequent oxidative esterification.

Language: Английский

Citations

26
Glycerol and its Derivatives as Potential C-3 Bio-based Building Blocks for Accessing Active Pharmaceutical Ingredients DOI
Romain Morodo,

Loïc Bovy,

Diana V. Silva-Brenes

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(19), P. 10029 - 10057

Published: Jan. 1, 2024

Exploring the potential of renewable glycerol and its derivatives for preparation active pharmaceutical ingredients in light regulatory constraints.

Language: Английский

Citations

2
Mild N‐Alkylation of Amines with Alcohols Catalyzed by the Acetate Ru(OAc)2(CO)(DiPPF) Complex DOI
Rosario Figliolia, Salvatore Baldino,

Hans Günter Nedden

et al.

Chemistry - A European Journal, Journal Year: 2017, Volume and Issue: 23(58), P. 14416 - 14419

Published: Aug. 31, 2017

The acetate complex Ru(OAc)2 (DiPPF) (2) obtained from (PPh3 )2 (1) and 1,1'-bis(diisopropylphosphino)ferrocene reacts cleanly with formaldehyde affording (CO)(DiPPF) (3) in high yield. monocarbonyl 3 (0.4-2 mol %) efficiently catalyzes the N-alkylation of primary secondary alkyl aromatic amines using alcohols ROH (R=Et, nPr, nBu, PhCH2 ) under mild reaction conditions (30-100 °C) an alcohol/amine molar ratio 10-100. Formation monohydride RuH(OAc)(CO)(DiPPF) (4) has been observed by iPrOH presence NEt3 at RT through equilibrium reaction.

Language: Английский

Citations

16
Development of a Mild and Efficient Process for Ir-Catalyzed N-Alkylation of 4-Bromopyridin-2-amine with a Primary Alcohol via Borrowing Hydrogen DOI
Sri Krishna Nimmagadda, K. Srinivas,

Siva Sankar Bondigela

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(8), P. 3414 - 3422

Published: July 25, 2024

We report herein the development and scale up of an Ir-catalyzed N-alkylation reaction between a 4-bromopyridin-2-amine (1) (4-(5-(1,1-difluoroethyl)-1,2,4-oxadiazol-3-yl)bicyclo[2.2.2]octan-1-yl)methanol (2) proceeding via borrowing hydrogen process. The traditional approach alcohol oxidation followed by reductive amination posed challenges that are attributed to poor nucleophilicity 2-aminopyridine derivative resulting in lower isolated yields. Several catalysts bases were evaluated for successful 1 with 2, Ir (III) catalyst combination LiOt-Bu as base was found provide optimal conversion. process successfully demonstrated on 1.5 kg afforded >70% yield 3 without need sealed reactor or any other specialized equipment.

Language: Английский

Citations

1
Molybdenum Complex-Catalyzed N-Alkylation of Bulky Primary and Secondary Amines DOI
Lingling Wang, Shahid Khan, Shahida Perveen

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16510 - 16521

Published: Nov. 4, 2024

Aliphatic allylic amines are present in a large number of complex and pharmaceutically relevant molecules. The direct amination electrophiles serves as the most common method toward preparation these motifs. However, use feedstock reaction components (allyl alcohol aliphatic amine) transformations remains great challenge. Such challenge primarily stems from high Lewis basicity steric hindrance amines, addition to low reactivity alcohols. Herein, we report general solution challenges. developed protocol allows an efficient allyl alcohols with sterically bulky presence inexpensive earth-abundant molybdenum complex. This simple economic also enables regioselective branched amination; practicality was shown efficient, scaled-up synthesis several drugs.

Language: Английский

Citations

1
Acetalization of glycerol with acetone over UAV-59 catalyst: Mild reaction conditions and enhanced selectivity DOI Creative Commons
I.C. Santos, Ricardo F. Mendes, Filipe A. Almeida Paz

et al.

Catalysis Today, Journal Year: 2023, Volume and Issue: 424, P. 114296 - 114296

Published: July 18, 2023

The solvent-free acetalization of glycerol with acetone was investigated using as catalyst UAV-59, a Coordination Polymer based on nitrilo(trimethylphosphonic acid) and Gd3+, at 25 °C 55 °C, various glycerol/acetone (Gly/Ace) molar ratios. reaction yielded solketal, five-membered acetal, 2,2-dimethyl-1,3-dioxan-5-ol, six-membered acetal. UAV-59's catalytic activity influenced by temperature, the highest conversion (94%) achieved 1/10 Gly/Ace ratio, 5% catalyst. selectivity for solketal remained consistent (95% - 98%) across all conditions. Reaction kinetics profiles were compared, stability assessed, results benchmarked against Metal Organic Framework catalysts from literature. heterogeneous nature catalysis confirmed through leaching tests, catalyst's chemical features analyzed ATR FT-IR spectra X-ray diffraction patterns, indicating that crystalline structure preserved during reaction.

Language: Английский

Citations

3
Glycerol-based ionic liquids: Crucial microwaves-assisted synthetic step for solketal amines DOI

Jean‐Pierre Mbakidi,

Sandrine Bouquillon

Journal of Molecular Liquids, Journal Year: 2017, Volume and Issue: 252, P. 218 - 224

Published: Dec. 21, 2017

Language: Английский

Citations

8
Ru‐Catalyzed Switchable N‐Hydroxyethylation and N‐Acetonylation with Crude Glycerol DOI
Xin Zhuo,

Le Jia,

Yuxing Huang

et al.

ChemSusChem, Journal Year: 2020, Volume and Issue: 13(8), P. 2007 - 2011

Published: Feb. 3, 2020

Abstract Highly efficient Ru‐catalyzed selective C−C or C−O bond cleavage of polyols (e.g., crude glycerol) for N ‐hydroxyethylation ‐acetonylation amines was achieved through the hydrogen‐borrowing approach. A variety were transformed to desired amino alcohols/ketones in moderate‐to‐excellent yields, opening up new avenues generation oxygenated pharmaceuticals and fine chemicals from renewable raw materials. The use redox‐active catalysts containing bisphosphine/thienylmethylamine ligands allows this system be operated selectively under both basic acidic conditions.

Language: Английский

Citations

8
Water-soluble meroterpenes containing an aminoglyceride fragment with geraniol residues: synthesis and membranotropic properties DOI
Alan Akhmedov, D. N. Shurpik,

Vitaliy V. Plemenkov

et al.

Mendeleev Communications, Journal Year: 2019, Volume and Issue: 29(1), P. 29 - 31

Published: Jan. 1, 2019

Language: Английский

Citations

7
Ruthenium Catalyzed N‐Alkylation of Cyclic Amines with Primary Alcohols DOI Creative Commons
Risto Savela, Dieter Vogt, Reko Leino

et al.

European Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 2020(20), P. 3030 - 3040

Published: April 16, 2020

A robust alcohol amination protocol using common saturated amines and primary alcohols as starting materials is described. The reactions are catalyzed by combination of dichloro( p ‐cymene)ruthenium(II) dimer precatalyst with triphenylphosphine ligand, the excess substrate or toluene functioning solvent. catalyst ligand residues can be precipitated from reaction media addition hexane cold diethyl ether, followed precipitation isolation product a hydrochloride salt.

Language: Английский

Citations

7