Diazines and Triazines as Building Blocks in Ligands for Metal-Mediated Catalytic Transformations

Doll, Julianna S.; Becker, Felix J.; Roşca, Dragoş-Adrian

doi:10.1021/acsorginorgau.3c00048

Cited by 4 publications

(2 citation statements)

References 162 publications

(136 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These findings demonstrate that higher N content in the Tta-Dfp framework (CHNS analysis, Table S4) is mainly responsible for NO 3 – and H + adsorption. Wherein, the abundant triazine and pyridine within Tta-Dfp units are known to act as Lewis base centers and can therefore facilitate the diffusion of both nitrates and protons (Lewis acid reactants) into the framework by acid–base interactions . There are multiple reports supporting the role of pyridine units as electrocatalytically active reaction centers for nitrate reduction, which is mainly responsible for NO 3 – and H + adsorption. , Among control COFs, Tab-Dfp has catalytic pyridine sites while it lacks nitrate and proton concentrators (triazine units) near catalytically active pyridine sites, and therefore, the catalytic activity becomes moderate.…”

Section: Electrocatalytic Performance For Nitrate Reduction Reaction ...mentioning

confidence: 99%

Covalent Organic Framework Bifunctional Catalyst for Glucose Oxidation Reaction Coupled Nitrate to Ammonia Electrolysis

Chaturvedi,

Gaber,

Kaur

et al. 2024

ACS Energy Lett.

View full text Add to dashboard Cite

Ammonia is a crucial feedstock for the chemical industry, a carbon-free energy source, and a safe source for hydrogen storage. The electrochemical nitrate reduction reaction (NO 3 RR) is one promising strategy for greener ammonia synthesis due to high water solubility and low N�O bond dissociation energy of NO 3 − . More importantly, polluted water is a source of NO 3 − . Herein, we rationally designed a bifunctional covalent organic framework catalyst (Ru-Tta-Dfp) having a triazine-and pyridine-rich backbone with inherent Ru-nanocluster sites to control both NO 3 − and H + diffusion and interactions to achieve selective conversion of NO 3 − to ammonia monitored by operando Raman spectroscopy (93.93% faradaic efficiency and yield rate of 1.16 mg h −1 cm −2 at −0.4 V vs RHE). Moreover, we have developed a strategy for the first time to couple the anodic glucose oxidation reaction (GOR) to facilitate the cathodic NO 3 RR with reduced energy consumption and to achieve value-added products at both electrodes. Notably, NO 3 RR-GOR full cell studies generate a ∼2.5 times higher NH 3 yield rate than that of NO 3 RR-OER.

show abstract

Section: Electrocatalytic Performance For Nitrate Reduction Reaction ...mentioning

confidence: 99%

Covalent Organic Framework Bifunctional Catalyst for Glucose Oxidation Reaction Coupled Nitrate to Ammonia Electrolysis

Chaturvedi,

Gaber,

Kaur

et al. 2024

ACS Energy Lett.

View full text Add to dashboard Cite

show abstract

“…Triazine-based tridentate polypyridyl ligand frameworks are well known for their efficacy in the field of catalysis as well as biology since the past several years. 47–50 The substituted N , N -dimethyl-4,6-di(pyridin-2-yl)-1,3,5-triazin-2-amine ligand with its ability to act both as a σ-donor and a strong π-acceptor ligand can be an ideal choice. 51 The presence of three electronegative nitrogen atoms in the central triazine ring allows it to store several redox equivalents within the ligand framework, promoting different oxidative and reductive transformations.…”

Section: Introductionmentioning

confidence: 99%

Triazine-based mononuclear copper(ii) cis-dichloro and dibromo complexes as functional biomimetic model systems for phenoxazinone synthase and catecholase activities

Roy,

Muley,

Mathur

et al. 2024

New J. Chem.

View full text Add to dashboard Cite

show abstract

Palladium-catalyzed cascade of aza-Wacker and Povarov reactions of aryl amines and 1,6-dienes for hexahydro-cyclopenta[b]quinoline framework

Wu,

Tan,

et al. 2024

Nat Commun

View full text Add to dashboard Cite

Palladium catalyzed tandem reaction represents a one-pot synthetic approach to efficiently synthesize complex functionalized molecules while reducing synthetic steps, aligning with the principles of green chemistry. However, achieving a direct cascade of the aza-Wacker and Povarov reactions in one-pot synthesis presents a challenge due to substrate compatibility issues between the two reactions. In this work, we describe an aza-Wacker/Povarov reaction employing a highly electrophilic palladium catalyst, which effectively converts anilines and 1,6-dienes into hexahydro-cyclopenta[b]quinolines. The optimized conditions yield up to 79%, with a diastereoselectivity > 20:1. Substrate range testing reveals compatibility with various sensitive functional groups, and successful late-stage modifications are performed on several natural products and drug molecules, demonstrating the versatility and practicality of the method. Additionally, a preliminary investigation into the reaction mechanism suggests an aza-Wacker process followed by a Povarov process.Transition metal catalysis represents a well-established and continually advancing field of research, providing a robust platform for the incorporation of oxygen-or nitrogen-containing functional groups onto readily available substrates such as alkynes and alkenes 1-5 . This methodology enables the efficient synthesis of valuable, complex, functionalized molecules in a cost-effective and expeditious manner. There is a challenge to balance the requirement for atom utilization, step economy, the demand for lengthy synthetic routes, reaction selectivity, and yield in the synthesis of complex molecules. Arranging and combining existing elementary ingeniously reactions in one-pot synthesis presents an effective strategy that concurrently addresses the need for rapid synthesis of complex molecular skeletons with high yields by decreasing the number of synthesis steps 6-10 .As a classic example of transition metal catalyzed reactions, the aza-Wacker reaction exhibits superior utility and versatility, particularly in the synthesis of natural products and bioactive compounds, with the Heck-type process typically serving as the primary subsequent transformation method (Fig. 1a) [11][12][13][14][15][16][17] . While the cascade cyclization reaction of dienes via an aminopalladation/Heck process has been reported [18][19][20][21][22][23][24][25][26] , further exploration is warranted to uncover more diverse subsequent reactions in series with the aza-Wacker process.To expand upon our previous investigations involving anilines and alkenes [27][28][29][30][31] , we aimed to diversify the range of reaction modes following the aza-Wacker process in a one-pot synthesis. Povarov reaction, characterized by mild conditions, excellent diastereoselectivity, and robust reaction compatibility, utilizing anilines, aldehydes, and alkenes as starting materials that overlap with the substrates or products of the aza-Wacker reaction, emerged as a promising candidate for the subsequent step following th...

show abstract

Diazines and Triazines as Building Blocks in Ligands for Metal-Mediated Catalytic Transformations

Cited by 4 publications

References 162 publications

Covalent Organic Framework Bifunctional Catalyst for Glucose Oxidation Reaction Coupled Nitrate to Ammonia Electrolysis

Covalent Organic Framework Bifunctional Catalyst for Glucose Oxidation Reaction Coupled Nitrate to Ammonia Electrolysis

Triazine-based mononuclear copper(ii) cis-dichloro and dibromo complexes as functional biomimetic model systems for phenoxazinone synthase and catecholase activities

Palladium-catalyzed cascade of aza-Wacker and Povarov reactions of aryl amines and 1,6-dienes for hexahydro-cyclopenta[b]quinoline framework

Contact Info

Product

Resources

About