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

Advances in One-Pot Synthesis through Borrowing Hydrogen Catalysis DOI
Avelino Corma, Javier Navas, María J. Sabater

et al.

Chemical Reviews, Journal Year: 2018, Volume and Issue: 118(4), P. 1410 - 1459

Published: Jan. 10, 2018

The borrowing hydrogen (BH) principle, also called auto-transfer, is a powerful approach which combines transfer hydrogenation (avoiding the direct use of molecular hydrogen) with one or more intermediate reactions to synthesize complex molecules without need for tedious separation isolation processes. strategy usually relies on three steps, (i) dehydrogenation, (ii) reaction, and (iii) hydrogenation, an excellent well-recognized process from synthetic, economic, environmental point view. In this context, objective present review give global overview topic starting those contributions published prior emergence BH concept most recent current research under term catalysis. Two main subareas (homogeneous heterogeneous catalysis) have been identified, subheadings based source electrophile (alkanes, alcohols, amines) considered. Then type bond being formed (carbon–carbon carbon heteroatom) has taken into account end-up reaction working in tandem metal-catalyzed hydrogenation/dehydrogenation step. completed advances asymmetric catalysis using strategy.

Language: Английский

Citations

876
Borrowing Hydrogen Amination Reactions: A Complex Analysis of Trends and Correlations of the Various Reaction Parameters DOI
Evgeniya Podyacheva, Oleg I. Afanasyev, Dmitry Vasilyev

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 7142 - 7198

Published: June 1, 2022

Borrowing hydrogen or the autotransfer amination is a powerful approach to create single C–N bonds, starting from stable and readily available substrates: amines alcohols. It considered as one of most atom-efficient green methods synthesize complex amines. Herein, we attempted arrange array existing data in comprehensive structured manner determine correlations between experimental conditions catalysis outcome both within different groups catalysts defined using machine analysis. For each type N-nucleophiles (aromatic, aliphatic, heteroaromatic amines, amides), efficient working were suggested, including attributing optimal base temperature regime for metal.

Language: Английский

Citations

83
Featuring Xantphos DOI
Piet W. N. M. van Leeuwen, Paul C. J. Kamer

Catalysis Science & Technology, Journal Year: 2017, Volume and Issue: 8(1), P. 26 - 113

Published: Nov. 7, 2017

This review highlights the use of bisphosphine ligand group in homogeneous catalysis.

Language: Английский

Citations

121
Cyclometalated Iridium Complex-Catalyzed N-Alkylation of Amines with Alcohols via Borrowing Hydrogen in Aqueous Media DOI Creative Commons
Nianhua Luo, Yuhong Zhong,

Hui‐Ling Wen

et al.

ACS Omega, Journal Year: 2020, Volume and Issue: 5(42), P. 27723 - 27732

Published: Oct. 19, 2020

This paper develops a methodology for cyclometalated iridium complex-catalyzed N-alkylation of amines with alcohols via borrowing hydrogen in the aqueous phase. The catalyst-mediated displays high activity (S/C up to 10,000 and yield 96%) ratio amine/imine (up >99:1) broad range substrates 46 examples) using water as green eco-friendly solvent. Most importantly, this transformation is simple, efficient, can be performed at gram scale, showcasing its potential industrially synthesizing N-alkylamine compounds.

Language: Английский

Citations

47
Morphology‐Tuned Activity of Ru/Nb2O5 Catalysts for Ketone Reductive Amination DOI
Wanjun Guo, Tao Tong, Xiaohui Liu

et al.

ChemCatChem, Journal Year: 2019, Volume and Issue: 11(16), P. 4130 - 4138

Published: April 18, 2019

Abstract Amines are important compounds in natural products and medicines. Specifically, cyclopentylamine is one of the value‐added chemicals widely used production pesticides, cosmetics In this work, three Ru/Nb 2 O 5 catalysts with different Nb morphologies were reductive amination cyclopentanone under mild reaction conditions (90 °C, MPa H ), among which 1 %Ru/Nb −L catalyst exhibits best performance yield reaching 84 %. This catalytic system stable has not significant deactivation even after runs durability test. addition, can be extended to a series aldehydes/ketones. Further comprehensive characterizations (XPS analysis CO‐adsorption DRIFT) reveal that electronic effect Ru species ruled out; instead, activity strongly influenced by geometric effect. Layered material possesses highest surface area, resulting dispersion, therefore shows activity. The in‐situ DRIFT‐MS technique was also understand mechanism. It found play key role activating carbonyl groups. study illustrates promising application ‐Layer synthesis amine provides an understanding

Language: Английский

Citations

46
Sustainable Amination of Bio-Based Alcohols by Hydrogen Borrowing Catalysis DOI Open Access
Sophie Hameury,

Hana Bensalem,

Karine De Oliveira Vigier

et al.

Catalysts, Journal Year: 2022, Volume and Issue: 12(11), P. 1306 - 1306

Published: Oct. 24, 2022

In this review, we aim to give an overview of the use Borrowing Hydrogen (BH) methodology with bio-based alcohols. This only forms water as a by-product, thus providing sustainable way amines, which have large range applications. process is particular interest when related biomass due high abundance alcohol functions in natural compounds. However, compounds often comprise multiple chemical that can change reactivity substrate. comprehensive comprising both homogeneous and heterogeneous catalysts, aims at summarizing recent advancements amination for every class substrate, highlighting key parameters governing their remaining scientific hurdles. Even though most substrates successfully been converted into corresponding reaction selectivity functional group tolerance still need be improved.

Language: Английский

Citations

25
Nanolayered cobalt–molybdenum sulphides (Co–Mo–S) catalyse borrowing hydrogen C–S bond formation reactions of thiols or H2S with alcohols DOI Creative Commons
Iván Sorribes, Avelino Corma

Chemical Science, Journal Year: 2019, Volume and Issue: 10(10), P. 3130 - 3142

Published: Jan. 1, 2019

Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These allow the preparation of a broad range thioethers in good to yields from structurally diverse thiols and readily available primary well secondary alcohols. Chemoselectivity presence sensitive groups such double bonds, nitriles, carboxylic esters halogens has demonstrated. It is also shown that reaction takes place through hydrogen-autotransfer (borrowing hydrogen) mechanism involves Co-Mo-S-mediated dehydrogenation hydrogenation reactions. A novel catalytic protocol based on thioetherification alcohols with hydrogen (H2S) furnish symmetrical developed using these earth-abundant metal-based catalysts.

Language: Английский

Citations

39
Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol‐Functionalized Phosphonium Salts DOI Creative Commons

Yuya Hu,

Zhihong Wei,

Anna Frey

et al.

ChemSusChem, Journal Year: 2020, Volume and Issue: 14(1), P. 363 - 372

Published: Oct. 17, 2020

Abstract A series of hydroxy‐functionalized phosphonium salts were studied as bifunctional catalysts for the conversion CO 2 with epoxides under mild and solvent‐free conditions. The reaction in presence a phenol‐based iodide proceeded via first order rection kinetic respect to substrate. Notably, contrast aliphatic analogue, catalyst showed no product inhibition. temperature dependence rate was investigated, activation energy model determined from an Arrhenius‐plot ( E =39.6 kJ mol −1 ). substrate scope also evaluated. Under optimized conditions, 20 terminal converted at room corresponding cyclic carbonates, which isolated yields up 99 %. is easily scalable performed on scale 50 g Moreover, this method applied synthesis antitussive agent dropropizine starting epichlorohydrin phenylpiperazine. Furthermore, DFT calculations rationalize mechanism high efficiency catalyst. calculation confirmed epoxide hydrogen bonding salt, facilitates ring‐opening step. effective Gibbs barrier regarding step 97 bromide 72 explains difference activity.

Language: Английский

Citations

33
Development and application of an efficient microplastics extraction method based on glycerol flotation for environmental soil samples DOI

Yingmiao Chen,

Muhammad Junaid,

Kai Yin

et al.

Gondwana Research, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

Citations

0
Utilizing Glycerol as an Ex Situ CO-Source in Pd-Catalyzed Alkoxycarbonylation of Styrenes DOI

Dorrit B. Nielsen,

Benjamin A. Wahlqvist, Dennis U. Nielsen

et al.

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(9), P. 6089 - 6093

Published: Aug. 10, 2017

We report on an efficient Ir-catalyzed decarbonylation of glycerol, which could be coupled to ensuing Pd-catalyzed alkoxycarbonylation styrenes. The formation hydrogen avoided by employing 1,4-benzoquinone (BQ) as external oxidant. A wide variety styrenes underwent the esterification in good yields and high regioselectivity. Applying catalytic amounts hexafluoroisopropanol provided access alcohols other than methanol, this transformation is often limited to. Finally, we demonstrate suitability methodology for preparation three well-known nonsteroidal anti-inflammatory drugs (NSAIDs).

Language: Английский

Citations

31