Synthesis of pyridinium ylides and simulation of their 1,3-dipolar cycloaddition mechanism

Radzhabov, Maxim R.; Tsyganov, Dmitriy V.; Pivina, T. S.; Krayushkin, M. M.; Seeboth, N.; Иванов, С. Н.; Salit, Anne-Frédérique

doi:10.1016/j.mencom.2017.09.025

Cited by 6 publications

(3 citation statements)

References 16 publications

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“…Pivina and co-authors recently reported quantum chemical calculations on the spatial and electronic structure of pyridinium ylides, as well as the modelling of their1,3-dipolar cycloadddition reactions. The results of computer modelling were in agreement with the experimental results [103]. However, as stated previously, this chapter will mainly report examples of the dearomatization reactions that allowed the formation of stable dihydropyridine derivatives.…”

Section: Pyridinium Ylidessupporting

confidence: 82%

Nucleophilic Dearomatization of Activated Pyridines

2018

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Amongst nitrogen heterocycles of different ring sizes and oxidation statuses, dihydropyridines (DHP) occupy a prominent role due to their synthetic versatility and occurrence in medicinally relevant compounds. One of the most straightforward synthetic approaches to polysubstituted DHP derivatives is provided by nucleophilic dearomatization of readily assembled pyridines. In this article, we collect and summarize nucleophilic dearomatization reactions of - pyridines reported in the literature between 2010 and mid-2018, complementing and updating previous reviews published in the early 2010s dedicated to various aspects of pyridine chemistry. Since functionalization of the pyridine nitrogen, rendering a (transient) pyridinium ion, is usually required to render the pyridine nucleus sufficiently electrophilic to suffer the attack of a nucleophile, the material is organized according to the type of N-functionalization. A variety of nucleophilic species (organometallic reagents, enolates, heteroaromatics, umpoled aldehydes) can be productively engaged in pyridine dearomatization reactions, including catalytic asymmetric implementations, providing useful and efficient synthetic platforms to (enantioenriched) DHPs. Conversely, pyridine nitrogen functionalization can also lead to pyridinium ylides. These dipolar species can undergo a variety of dipolar cycloaddition reactions with electron-poor dipolarophiles, affording polycyclic frameworks and embedding a DHP moiety in their structures.

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Section: Pyridinium Ylidessupporting

confidence: 82%

Nucleophilic Dearomatization of Activated Pyridines

2018

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“…Consequently, the charge transfer will take place from dipole to dipolarophiles this in accordance with other pyridinium ylides. [ 5 ]…”

Section: Resultsmentioning

confidence: 99%

“…Pyridinium ylides can be successfully engaged in 1,3-dipolar cycloadditions, which is one of the most convenient methods for the synthesis of five-membered heterocycles. [3][4][5] In the case of 1,3-dipolar cycloadditions, the obtained products, displaying partially reduced indolizine backbones, may then be converted to proper indolizines by oxidation, or into indolizidines by reduction or other types of functionalization. [3] The reaction is a [3 + 2] cycloaddition, where the numbers 3 and 2 represent the pi electron counts of the conjugated diene and dienophile.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Almutaleb

Al‐abbasi

2022

J of Physical Organic Chem

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In this article, we present advances related to 1,3‐dipolar cycloadditions of generated pyridinium ylides and apply these results to specific 1,3‐dipolar cycloaddition reactions with oxindole dipolarophiles. The ylide discussed in this article is generated from alkylation reactions between substituted pyridines and a primary electrophile. Cycloaddition reactions proceeding from pyridinium ylides and various oxindoles are reported with good stereo‐ and regioselectivity. Cycloaddition reactions take place by the overlap of the HOMO of the dipole and the LUMO of the dipolarophile when the two orbitals have similar energies, resulting in the formation of two new bonds. To get more insight into the reaction nature, a quantum chemical simulation was performed. A computational study is performed on the reactants (pyridinium ylides and oxindoles) and resulting cycloadducts. The present analysis reveals that the cycloaddition reactions under study can be classified in the normal electron demand category. Regioselectivity and mechanism of 1,3‐cycloaddition reactions are studied in the light of several theoretical approaches such as activation energy, Houk's rule based on the FMO theory, and the DFT reactivity indices.

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Reactions of 3а,6a-diaza-1,4-diphosphapentalene with activated acetylenes

et al. 2018

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Synthesis of pyridinium ylides and simulation of their 1,3-dipolar cycloaddition mechanism

Cited by 6 publications

References 16 publications

Nucleophilic Dearomatization of Activated Pyridines

Nucleophilic Dearomatization of Activated Pyridines

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Reactions of 3а,6a-diaza-1,4-diphosphapentalene with activated acetylenes

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Synthesis of pyridinium ylides and simulation of their 1,3-dipolar cycloaddition mechanism

Cited by 6 publications

References 16 publications

Nucleophilic Dearomatization of Activated Pyridines

Nucleophilic Dearomatization of Activated Pyridines

Synthesis, characterization and computational studies for (2′S*,3R*,3′S*,8a′R*)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives

Reactions of 3а,6a-diaza-1,4-diphosphapentalene with activated acetylenes

Contact Info

Product

Resources

About

Synthesis, characterization and computational studies for (2′S,3R,3′S,8a′R)‐2′,3′‐bis(ethoxycarbonyl)‐2‐oxo‐2′,3′‐dihydro‐8a′H‐spiro[indoline‐3,1′‐indolizine]‐6′‐carboxylic acid and some derivatives