A Cooperative Cobalt-Driven System for One-Carbon Extension in the Synthesis of (Z)-Silyl Enol Ethers from Aldehydes: Unlocking Regio- and Stereoselectivity DOI Creative Commons
Soumyashree Jena,

Lars Frenzen,

Vishal Chugh

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(51), P. 27922 - 27932

Published: Dec. 12, 2023

The research presented herein explores a cobalt-based catalytic system, distinctively featuring cooperative boron-centric element within its intricate ligand architecture. This system is strategically engineered to enable the integration of singular carbon atom into aldehydes, process culminating in production (Z)-silyl enol ethers. Beyond offering an efficient one-pot synthesis route, this method adeptly overcomes challenges inherent conventional techniques, such as need for large amounts additives, restrictive functional group tolerance, and extreme reaction temperatures. Initial mechanistic studies suggest potential role cobalt–carbene complex catalytically significant species underscore importance borane segment. Collectively, these observations highlight advancing bond activation pursuits.

Language: Английский

Challenges and recent advancements in the transformation of CO2into carboxylic acids: straightforward assembly with homogeneous 3d metals DOI
Robin Cauwenbergh, Vishakha Goyal, Rakesh Maiti

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(22), P. 9371 - 9423

Published: Jan. 1, 2022

The transformation of carbon dioxide (CO2) into useful chemicals, advanced materials, and energy is a long-standing challenge in both fundamental science industry. In recent years, utilization CO2 the presence inexpensive non-negligible environmentally friendly 3d metal-based catalysts (Fe, Mn, Co, Ni, Cu Ti) has become one most attractive topics. Particular attention been given to synthesis carboxylic acids their derivatives since these molecules serve as key intermediates chemical, fertilizer, pharmaceutical sectors. Considering numerous challenges linked with reactivity, number research groups have recently focused on by following thermo-, photo-, electrochemical strategies. However, facile access such remains vital catalysis organic owing high stability molecule which atom highest oxidation state. Another hurdle solve selectivity issue caused reaction different catalytic systems reactive functional group-containing molecules. Despite all issues, wide range transition applied this direction, but cheaper price inherent metals are at forefront domain. these, we aim summarise advances (over past five years) 3d-metal complexes reactivity towards activation for acids. Furthermore, discuss current trends, knowledge gaps, invigorating perspectives future advances.

Language: Английский

Citations

80
Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde DOI Creative Commons
Siqi Zhao, Hong‐Qing Liang, Xin‐Ming Hu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 6, 2022

Formaldehyde (HCHO) is a crucial C

Language: Английский

Citations

42
Unraveling the role of basic sites in the hydrogenation of CO2 to formic acid over Ni-based catalysts DOI
Yixuan Wang,

Hong-Yan Ban,

Yugao Wang

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 430, P. 115357 - 115357

Published: Feb. 1, 2024

Language: Английский

Citations

16
Selective Reduction of CO2 to Methanol via Hydrosilylation Boosted by a Porphyrinic Metal–Organic Framework DOI
Chunying Chen, Qijie Mo, Yongsheng Huang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6837 - 6845

Published: May 4, 2023

Methanol has been widely used in organic synthesis and fuel fields. The capture selective reduction of CO2 to methanol can not only decrease concentrations but also produce as a value-added chemical fuel. Herein, the via hydrosilylation was reported be accelerated by porphyrinic metal–organic framework (Ir-PCN-222). Catalytic results showed that Ir-PCN-222 efficient for reduction. Under atmospheric pressure, turnover frequency up 157 h–1 number could reach 1875 with catalyst. catalytic reactions accomplished under low concentration (15% 85% N2) more than 99% conversion selectivity. reaction mechanism studied density functional theory calculations molecular dynamics simulations, revealing balance between hydrosilanes around catalytically active iridium porphyrin units confined spaces played an important role product

Language: Английский

Citations

17
Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation DOI Creative Commons
Vincent Porte, Miljan N. M. Milunović,

Ulrich Knof

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(3), P. 1166 - 1183

Published: March 12, 2024

Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical redox noninnocence pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series cobalt has been studied by range methods, including spectroscopy [UV–vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption (XAS)], cyclic voltammetry, diffraction, density functional theory (DFT) calculations. Two [CoIII(H2LSMe)I]I [CoIII(LSMe)I2] were found to act as precatalysts Wacker-type oxidation olefins using phenylsilane, the role which was elucidated through isotopic labeling. Insights into mechanism transformation well substrate scope this selective reaction described, essential phenylsilane PBIT disclosed. Among several relevant species characterized an unprecedented Co(III) complex dianionic diradical ligand ([CoIII(LSMe••)I]).

Language: Английский

Citations

7
Efficient hydrogenation of CO2 to formic acid in water without consumption of a base DOI
Wentao Ma,

Jinling Hu,

Lei Zhou

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(17), P. 6727 - 6732

Published: Jan. 1, 2022

CO 2 hydrogenation to formic acid was achieved without consumption of a base and turnover number up 364 249 obtained. HCOOH is isolatable the catalyst–base system easily recycled.

Language: Английский

Citations

24
An Adaptive Rhodium Catalyst to Control the Hydrogenation Network of Nitroarenes DOI Creative Commons
Vishal Chugh, Basujit Chatterjee, Wei‐Chieh Chang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: June 27, 2022

An adaptive catalytic system that provides control over the nitroarene hydrogenation network to prepare a wide range of aniline and hydroxylamine derivatives is presented. This takes advantage delicate interplay between rhodium(III) center Lewis acidic borane introduced in secondary coordination sphere metal. The high chemoselectivity catalyst presence various potentially vulnerable functional groups its readiness be deployed at preparative scale illustrate practicality. Mechanistic studies density theory (DFT) methods were used shed light on mode functioning elucidate origin adaptivity. competition for interaction with boron solvent molecule substrate was found crucial When operating THF, reduction stops platform, whereas reaction can directed platform toluene.

Language: Английский

Citations

23
Theory-guided development of homogeneous catalysts for the reduction of CO2to formate, formaldehyde, and methanol derivatives DOI Creative Commons
Hanna H. Cramer, Shubhajit Das, Matthew D. Wodrich

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(11), P. 2799 - 2807

Published: Jan. 1, 2023

Computational volcano plots are used to predict selectivity in the context of (first-row) transition metal-catalyzed CO 2 reduction. The expected trends were tested experimentally and allowed for systematic improvement catalyst.

Language: Английский

Citations

15
Cobalt-catalyzed dehydrogenative cross-coupling reaction: Selective access to dihydrosiloxanes, hydrosiloxanes and functionalized silsesquioxanes DOI Creative Commons
Ewelina Szafoni, Krzysztof Kuciński, Grzegorz Hreczycho

et al.

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 423, P. 1 - 9

Published: April 27, 2023

Disclosed is a mild, scalable, and chemoselective cross-dehydrogenative functionalization protocol for the construction of Si−O−Si moieties under cobalt catalysis. The reaction has broad scope can be used to synthesize wide range silicon building blocks, including challenging dihydrosiloxanes functionalized silsesquioxanes. Most importantly, results are placed into context by benchmarking with state-of-the-art methods. Remarkably, utilized PNP-Co catalyst enables development further synthetic strategies such as one-pot sequential silanolysis/alcoholysis process or unprecedented dehydrocoupling between germanol hydrosilane.

Language: Английский

Citations

13
Co‐catalyzed Selective syn‐Hydrosilylation of Internal Alkynes DOI Creative Commons
Hanna Stachowiak, Krzysztof Kuciński, Bożena Wyrzykiewicz

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(14)

Published: May 30, 2023

Abstract Vinylsilanes are highly appealing and convenient chemical derivatives, as evidenced by the increasing number of synthetic transformations utilizing this class compounds. Herein, a new comprehensive cobalt‐catalyzed procedure has been developed enabling selective hydrosilylation internal aryl‐, alkyl‐, silylalkynes. Cobalt complexes bearing triazine‐based PNP pincer‐type ligands provide exclusive syn ‐addition primary well secondary silanes to C≡C bonds. As result, ( E )‐silylalkenes vicinal disilylalkenes were effectively obtained with excellent stereoselectivity regioselectivity. Unlike several TM‐catalyzed procedures, no external additives required since hydrosilanes act both substrates activators.

Language: Английский

Citations

13