Highly Efficient Thiolate‐Based Ionic Liquid Catalysts for Reduction of CO2: Selective N‐Functionalization of Amines to Form N‐Formamides and N‐Methylamines DOI
Jiakai Wu,

Junping Niu,

Lu Hou

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(32)

Published: April 6, 2024

Abstract Developing efficient catalysts to convert CO 2 into value‐added chemicals is valuable for reducing carbon emissions. Herein, a kind of novel thiolate‐based ionic liquid with sulfur as the active site was designed and synthesized, which served highly catalyst reductive N‐functionalization by amines hydrosilane. By adjusting pressure, various N‐formamides N‐methylamines were selectively obtained in high yields. Remarkably, at loading 0.1 mol %, N‐formylation reaction N ‐methylaniline exhibited an impressive turnover frequency (TOF) up 600 h −1 , could be attributed roles liquids activating hydrosilane amine. In addition, control experiments NMR monitoring provided evidence that reduction yielded formoxysilane intermediates subsequently reacted form N‐formylated products. Alternatively, further react amine produce 4‐electron‐reduced aminal These products crucial N‐methylation reactions.

Language: Английский

Secondary Sphere Effects on Porous Polymeric Organocatalysts for CO2 Transformations: Subtle Modifications Resulting in Superior Performance DOI
Yanpei Song, Qi Sun, Pui Ching Lan

et al.

ACS Applied Materials & Interfaces, Journal Year: 2020, Volume and Issue: 12(29), P. 32827 - 32833

Published: June 29, 2020

Albeit harnessing secondary sphere interactions to exert control over the reaction outcomes has primarily been applied enzymatic and organometallic catalysis, there are seldom any studies that introduce outer-sphere modifiers into organocatalysts. This is even less in corresponding heterogeneous catalytic system. In this contribution, we experimentally computationally investigate role of effects reactivity bromide anions toward CO2 transformations. Six pyridinium cationic porous frameworks have synthesized fully characterized. Structure–activity relationships kinetics show type location substituents on framework a significant impact nucleophilic their counter anion. Specifically, attachment amine substituent ortho position relative motif produces remarkably efficient catalyst for transformation, by factor six times greater comparison pristine pyridinium-based polymer. The hydrogen-bond-interaction-promoted reagent activation enhanced delocalization ability anion believed be key driving utilization. These observations, therefore, champion leverage interaction optimizing

Language: Английский

Citations

32
Recent Advances in the Chemistry of Metal Carbamates DOI Creative Commons
Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni

et al.

Molecules, Journal Year: 2020, Volume and Issue: 25(16), P. 3603 - 3603

Published: Aug. 7, 2020

Following a related review dating back to 2003, the present discusses in detail various synthetic, structural and reactivity aspects of metal species containing one or more carbamato ligands, representing large family compounds across all periodic table. A preliminary overview is provided on carbon dioxide with amines, emphasis given recent findings concerning applications fields.

Language: Английский

Citations

32
Mechanistic insights into carbamate formation from CO2and amines: the role of guanidine–CO2adducts DOI Creative Commons
Jere K. Mannisto, Ljiljana Pavlovic, Tony Tiainen

et al.

Catalysis Science & Technology, Journal Year: 2021, Volume and Issue: 11(20), P. 6877 - 6886

Published: Jan. 1, 2021

This work explores the reactivity of a reversible superbase–CO 2 zwitterion, which can be used as stoichiometric source CO .

Language: Английский

Citations

25
Highly Efficient Conversion of Propargylic Alcohols and Propargylic Amines with CO2 Activated by Noble‐Metal‐Free Catalyst Cu2O@ZIF‐8 DOI

Ai‐Ling Gu,

Yaxin Zhang, Zhi‐Lei Wu

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(19)

Published: Jan. 11, 2022

Abstract The cyclization reactions of propargylic alcohols and amines with CO 2 are important in industrial applications, but it was a great challenge that non‐noble‐metal catalysts catalyzed both under mild conditions. Herein, the catalyst Cu O@ZIF‐8 prepared by encapsulating O nanoparticles into robust ZIF‐8, can effectively catalyze valuable α‐alkylidene cyclic carbonates oxazolidinones turnover numbers (TONs) 12.1 19.6, which be recycled at least five times. mechanisms were further uncovered NMR, FTIR, 13 C isotope‐labeling experiments DFT calculations, DBU synergistically activate C≡C bond hydroxy/amino group substrates. Importantly, is first example noble‐metal‐free simultaneously.

Language: Английский

Citations

17
Highly Efficient Thiolate‐Based Ionic Liquid Catalysts for Reduction of CO2: Selective N‐Functionalization of Amines to Form N‐Formamides and N‐Methylamines DOI
Jiakai Wu,

Junping Niu,

Lu Hou

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(32)

Published: April 6, 2024

Abstract Developing efficient catalysts to convert CO 2 into value‐added chemicals is valuable for reducing carbon emissions. Herein, a kind of novel thiolate‐based ionic liquid with sulfur as the active site was designed and synthesized, which served highly catalyst reductive N‐functionalization by amines hydrosilane. By adjusting pressure, various N‐formamides N‐methylamines were selectively obtained in high yields. Remarkably, at loading 0.1 mol %, N‐formylation reaction N ‐methylaniline exhibited an impressive turnover frequency (TOF) up 600 h −1 , could be attributed roles liquids activating hydrosilane amine. In addition, control experiments NMR monitoring provided evidence that reduction yielded formoxysilane intermediates subsequently reacted form N‐formylated products. Alternatively, further react amine produce 4‐electron‐reduced aminal These products crucial N‐methylation reactions.

Language: Английский

Citations

3