DFT and AFIR study on the copper(<scp>i</scp>)-catalyzed mechanism of 5-enamine-trisubstituted-1,2,3-triazole synthesis <i>via</i> C–N cross-coupling and the origin of ring-opening of 2<i>H</i>-azirines

Yu, Fan; Zhou, Zhaoman; Song, Jiajia; Zhao, Yanying

doi:10.1039/d0ra07498e

Cited by 5 publications

(3 citation statements)

References 72 publications

(78 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compared with these interrupted click reaction, copper(I)-catalyzed one-pot synthesis of fully substituted enamine-functionalized 1,2,3triazoles via azide, terminal alkyne, and 2H-azirine, especially featuring without 1,4-disubstituted 1,2,3-triazole byproduct. [83] Based on density functional theory (DFT) and multicomponent artificial force-induced reaction (MCÀ AFIR) methods, Zhao and co-workers [84] have demonstrated that the reaction proceeds through (1) thermodynamically di-copper catalyzed cleavage of CÀ N single bond of 2H-azirines, (2) alkyne hydrogen atom transfer, (3) [3 + 2] ring cycloaddition, and (4) reductive elimination to form CÀ N bond (Scheme 51a).…”

Section: Synthesis Of Nxy-containing Heterocyclesmentioning

confidence: 99%

2H‐Azirines: Recent Progress in Synthesis and Applications

Xu,

Zeng,

Luo

et al. 2024

Eur J Org Chem

View full text Add to dashboard Cite

2H‐arizines are important three‐membered heterocycles in organic chemistry. Recently, many advances in the synthesis and functionalization of 2H‐arizines have been reported. Neber rearrangement, isomerization of isoxazole, oxidation of enamine, C–H bond activation, decomposition of vinyl azide, functionalization of alkyne, and multi‐step synthesis have been developed for the efficient assembly of 2H‐azirines. As versatile and highly strained three‐membered unsaturated heterocycles, 2H‐azirines can be used as distinctive building blocks towards significant functional groups, and have attracted extensive attention for the fabrication of numerous heterocycles. Recent studies have focused on [3+n] ring‐expansion reactions, nucleophilic addition of C=N double bond or continuous nucleophilic addition followed by cyclization, ring‐opening of 2H‐azirines to acyclic compounds, and substitution of sp3‐C‐H of 2H‐azirines. One of the most critical challenges is seeking for a selective opening of the specific three bonds of the strained azirine circle, some of what can be achieved on the basis of metal catalyst, photocatalysis, or combination of metal catalyst and photocatalysis. In this review, recent advances involving the synthesis and reactivity of 2H‐arizines accompanied with challenges and breakthroughs are summarized. The review mainly covers the period from 2019 to 2023.

show abstract

Section: Synthesis Of Nxy-containing Heterocyclesmentioning

confidence: 99%

2H‐Azirines: Recent Progress in Synthesis and Applications

Xu,

Zeng,

Luo

et al. 2024

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…Multimolecular reaction paths can be successfully followed using the artificial force-induced reaction (AFIR) method, − which directs the transitions from one equilibrium structure to another by applying splitting or merging force to two interacting fragments. This approach was used to automatically construct the catalytic paths for various homogeneous catalytic reactions with transition metal complexes. − …”

Section: Introductionmentioning

confidence: 99%

ReNeGate: A Reaction Network Graph-Theoretical Tool for Automated Mechanistic Studies in Computational Homogeneous Catalysis

Hashemi

Bougueroua

Gaigeot

et al. 2022

J. Chem. Theory Comput.

View full text Add to dashboard Cite

Exploration of the chemical reaction space of chemical transformations in multicomponent mixtures is one of the main challenges in contemporary computational chemistry. To remove expert bias from mechanistic studies and to discover new chemistries, an automated graph-theoretical methodology is proposed, which puts forward a network formalism of homogeneous catalysis reactions and utilizes a network analysis tool for mechanistic studies. The method can be used for analyzing trajectories with single and multiple catalytic species and can provide unique conformers of catalysts including multinuclear catalyst clusters along with other catalytic mixture components. The presented three-step approach has the integrated ability to handle multicomponent catalytic systems of arbitrary complexity (mixtures of reactants, catalyst precursors, ligands, additives, and solvents). It is not limited to predefined chemical rules, does not require prealignment of reaction mixture components consistent with a reaction coordinate, and is not agnostic to the chemical nature of transformations. Conformer exploration, reactive event identification, and reaction network analysis are the main steps taken for identifying the pathways in catalytic systems given the starting precatalytic reaction mixture as the input. Such a methodology allows us to efficiently explore catalytic systems in realistic conditions for either previously observed or completely unknown reactive events in the context of a network representing different intermediates. Our workflow for the catalytic reaction space exploration exclusively focuses on the identification of thermodynamically feasible conversion channels, representative of the (secondary) catalyst deactivation or inhibition paths, which are usually most difficult to anticipate based solely on expert chemical knowledge. Thus, the expert bias is sought to be removed at all steps, and the chemical intuition is limited to the choice of the thermodynamic constraint imposed by the applicable experimental conditions in terms of threshold energy values for allowed transformations. The capabilities of the proposed methodology have been tested by exploring the reactivity of Mn complexes relevant for catalytic hydrogenation chemistry to verify previously postulated activation mechanisms and unravel unexpected reaction channels relevant to rare deactivation events.

show abstract

“…This approach was used to automatically construct the catalytic paths for various homogeneous catalytic reactions with transition metal complexes. [24][25][26] Despite being highly systematic, such curvature-based exploration strategies may be impractical to studying very large and complex catalytic systems. By introducing principles of algorithmic search, the efficiency of the path-finding for the conversion of a given substrate state to a defined product state can be substantially improved.…”

Section: Introductionmentioning

confidence: 99%

ReNeGate: Reaction Network Graph Theoretical tool for automated mechanistic studies in computational homogeneous catalysis

Hashemi

Bougueroua

Gaigeot

et al. 2022

Preprint

View full text Add to dashboard Cite

Exploration of the chemical reaction space of chemical transformations in multicomponent mixtures is a challenge for modern computational protocols. In order to remove expert bias from mechanistic studies and to discover new chemistries, an automated graph-theoretical methodology is proposed to provide mechanistic analysis in catalytic systems. The primary advantage of the presented three-step approach over the existing automated pathways generation methods is the integrated ability to handle multicomponent catalytic systems of arbitrary complexity (mixtures of reactants, catalyst precursors, ligands, additives, and solvent). It is not limited to pre-defined chemical rules, does not require pre-alignment of reaction mixture components consistent with a reaction coordinate and is not agnostic to the chemical nature of transformations. Conformer exploration, Reactive event identification and Reaction network analysis are the main steps taken for understanding the underlying mechanistic pathways in catalytic mixtures given the reaction mixture as the input. Such a methodology allows to comprehensively explore the catalytic systems in realistic conditions for either previously observed or completely unknown reactive events. The expert bias is sought to be removed in either of the steps and chemical intuition is limited to the choice of the thermodynamic constraint imposed by the applicable experimental conditions in terms of threshold energy values for allowed transformations. The capabilities of the proposed methodology have been tested by exploring reactivity of Mn complexes relevant for catalytic hydrogenation chemistry to verify previously postulated activation mechanisms and unravel unexpected reaction channels relevant to rare deactivation events.

show abstract

DFT and AFIR study on the copper(i)-catalyzed mechanism of 5-enamine-trisubstituted-1,2,3-triazole synthesis via C–N cross-coupling and the origin of ring-opening of 2H-azirines

Abstract: The Cu(i)-catalyzed mechanism of 5-enamined-functionalized fully substituted 1,2,3-triazole synthesis was rationalized by interrupted copper(i)-catalyzed terminal alkynes and organic azides click reaction (CuAAC).

Cited by 5 publications

References 72 publications

2H‐Azirines: Recent Progress in Synthesis and Applications

2H‐Azirines: Recent Progress in Synthesis and Applications

ReNeGate: A Reaction Network Graph-Theoretical Tool for Automated Mechanistic Studies in Computational Homogeneous Catalysis

ReNeGate: Reaction Network Graph Theoretical tool for automated mechanistic studies in computational homogeneous catalysis

Contact Info

Product

Resources

About