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

Advancements and Challenges in Reductive Conversion of Carbon Dioxide via Thermo-/Photocatalysis DOI
Liqi Qiu,

Xiangyang Yao,

Yongkang Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(8), P. 4942 - 4964

Published: Nov. 7, 2022

Carbon dioxide (CO2) is the major greenhouse gas and also an abundant renewable carbon resource. Therefore, its chemical conversion utilization are of great attraction for sustainable development. Especially, reductive CO2 with energy input has become a current hotspot due to ability access fuels various important chemicals. Nowadays, controllable hydrogenation formic acid alcohols using H2 resources been regarded as appealing solution hydrogen storage accumulation. In addition, photocatalytic reduction CO provides potential way utilize this efficiently. Besides direct hydrogenation, functionalization integrates subsequent C–X (X = N, S, C, O) bond formation indirect transformation strategies, enlarging diverse products derived from promoting into new stage. Perspective, progress challenges conversion, including functionalization, reduction, summarized discussed along key issues future trends/directions in field. We hope Perspective can evoke intense interest inspire much innovation promise valorization.

Language: Английский

Citations

28
A polymeric ionic liquid catalyst for the N-formylation and N-methylation of amines using CO2/PhSiH3 DOI Creative Commons
Aswin Gopakumar, Loris Lombardo, Zhaofu Fei

et al.

Journal of CO2 Utilization, Journal Year: 2020, Volume and Issue: 41, P. 101240 - 101240

Published: July 8, 2020

We describe a polymeric ionic liquid (PIL) derived from trimethyl(p-vinylbenzyl)ammonium chloride ([VBTAm]Cl) that efficiently catalyzes the N-formylation of amines employing CO2 and PhSiH3 at room temperature with low catalyst loadings in near-quantitative yield. Under more forcing conditions N-methylated products can be selectively obtained. The PIL easily recovered reused repeatedly without decrease activity. reaction mechanism was studied situ using high-pressure NMR spectroscopy tentative mechanistic cycle has been proposed.

Language: Английский

Citations

34
Selective Reductive Dimerization of CO2 into Glycolaldehyde DOI
Dan Zhang, Carlos Jarava‐Barrera, Sébastien Bontemps

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(8), P. 4568 - 4575

Published: March 31, 2021

The selective dimerization of CO2 into glycolaldehyde is achieved in a one-pot two-step process via formaldehyde as key intermediate. first step concerns the iron-catalyzed reduction formation and controlled hydrolysis bis(boryl)acetal compound. second carbene-catalyzed C–C bond to afford glycolaldehyde. Both carbon atoms arise from proven by labeling experiment with 13CO2. This hybrid organometallic/organic catalytic system employs mild conditions (1 atm CO2, 25 80 °C less than 3 h) low loadings 2.5%, respectively). Glycolaldehyde obtained 53% overall yield. appealing reactivity exemplified (i) leading C4 aldose compounds (ii) tri-component Petasis–Borono–Mannich reaction generating C–N bonds one process.

Language: Английский

Citations

30
Access to N−CF3 Formamides by Reduction of N−CF3 Carbamoyl Fluorides DOI Creative Commons

Filip G. Zivkovic,

Christian D.‐T. Nielsen, Franziska Schoenebeck

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(52)

Published: Oct. 29, 2022

Abstract The departure into unknown chemical space is essential for the discovery of new properties and function. We herein report first synthetic access to N ‐trifluoromethylated formamides. method involves reduction bench‐stable CF 3 carbamoyl fluorides characterized by operational simplicity mildness, tolerating a broad range functional groups as well stereocenters. newly made −CF formamide motif proved be highly robust compatible with diverse transformations, underscoring its potential building block in complex molecules.

Language: Английский

Citations

22
Water Activation Triggered by Cu−Co Double‐Atom Catalyst for Silane Oxidation DOI
Ping Zhang, Teng Li, Xingchao Dai

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 6, 2023

Abstract High‐performance catalysts sufficient to significantly reduce the energy barrier of water activation are crucial in facilitating reactions that restricted by dissociation. Herein we present a Cu−Co double‐atom catalyst (CuCo‐DAC), which possesses uniform and well‐defined CuCoN 6 (OH) structure, works together promote silane oxidation. The achieves superior catalytic performance far exceeding single‐atom (SACs). Various functional silanes converted into silanols with up 98 % yield 99 selectivity. Kinetic studies show oxidation CuCo‐DAC is lower than Cu (Cu‐SAC) Co (Co‐SAC). Theoretical calculations demonstrate two different reaction pathways where splitting rate‐determining step it accelerated CuCo‐DAC, whereas H 2 formation key for its counterpart.

Language: Английский

Citations

11
Selective N-monomethylation of amines using CO2/H2 catalyzed by high-activity Cu–ZrO interface on SBA-15 DOI
Y. Xie, Yingjie Lai, Xiaohong Wu

et al.

Applied Surface Science, Journal Year: 2024, Volume and Issue: 654, P. 159399 - 159399

Published: Jan. 21, 2024

Language: Английский

Citations

4
Aerobic Oxidative Synthesis of Formamides from Amines and Bioderived Formyl Surrogates DOI Creative Commons
Xingchao Dai, Yunyan Han, Haijun Jiao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 3, 2024

Herein we present a new strategy for the oxidative synthesis of formamides from various types amines and bioderived formyl sources (DHA, GLA GLCA) molecular oxygen (O

Language: Английский

Citations

4
Cobalt-Cluster-Based Metal–Organic-Framework-Catalyzed Carboxylative Cyclization of Propargylic Amines with CO2 from Flue Gas DOI

Meng-Hua Tang,

Yan Wang, Zhi Fang

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

The fixation of carbon dioxide (CO2) directly from flue gas into valuable chemicals like 2-oxazolidinones is great significance for economic and environmental benefits, which typically catalyzed by noble-metal catalysts under harsh conditions. Herein, a novel 2-fold interpenetrated framework {[Co3(μ2-O)(TCA)2(HDPTA)2]·2H2O·2DMF}n [Co(II)-based metal-organic (Co-MOF)] containing [Co3] clusters highly dense amino groups (-NH2) dispersed in the channel was prepared, exhibiting high solvent/pH stability CO2 adsorption capacity (24.9 cm3·g-1). Catalytic experiments demonstrated that Co-MOF could catalyze carboxylative cyclization propargylic amines to generate with yields up 98% mild conditions gas. In addition, retained its structure catalytic activity after five-cycle experiments, showing promising practical application. Density functional theory (DFT) calculation suggested centers MOF activated C≡C much more binding energy than Co(NO3)2, partly accounting Co-MOF. This work demonstrates first Co-based material efficient as source, inspiring further rational design porous utilization.

Language: Английский

Citations

0
Mild oxidative N-formylation of amines with biobased glycolaldehyde over C3N4 supported Cu catalyst under green solvent DOI
Xingchao Dai, Yunyan Han, Haijun Jiao

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: 508, P. 160963 - 160963

Published: Feb. 27, 2025

Language: Английский

Citations

0
Iridium-Catalyzed, Copper-Induced Reductive Cyclization of NO2-Pyrrolarenes with CO2 as a Single-Carbon Source DOI
Qiang Yan, Jiang Nan, Lanxin Zhu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

A new catalytic conversion type of nitro substrate with CO2 as a single-carbon source is presented, wherein great collection azaheterocycles generated by newly established iridium-catalyzed, copper-induced reductive system. This procedure handily employs poly(methylhydrosiloxane) (PMHS) the reductant to simultaneously realize dual reduction highest oxidation-state and units in one operation. Elaborate mechanistic studies illustrate essential role iridium catalyst reducing NO2 moiety well double functions copper additive subsequent formylation C-H cyclization steps.

Language: Английский

Citations

0