Reactions of 4-Pyrones with Azomethine Ylides as a Chemo­selective Method for the Construction of Multisubstituted Pyrano[2,3-c]pyrrolidines

Synthesis ◽  
2021 ◽  
Author(s):  
Dmitrii L. Obydennov ◽  
Vyacheslav D. Steben’kov ◽  
Konstantin L. Obydennov ◽  
Sergey A. Usachev ◽  
Vladimir S. Moshkin ◽  
...  
Keyword(s):  
Double Bond ◽  
Ring Opening ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Computational Studies ◽  
Carbon Double Bond ◽  
Reactivity Indexes ◽  
Reaction Proceeds

Abstract4-Pyrones bearing electron-donating and electron-withdrawing groups react with nonstabilized azomethine ylides to form pyrano[2,3-c]pyrrolidines in moderate to good yields. The reaction proceeds chemoselectively as a 1,3-dipolar cycloaddition of the azomethine ylide at the carbon–carbon double bond of the pyrone activated by the electron-withdrawing substituent. The reactivity of 4-pyrones toward azomethine ylides was rationalized by computational studies with the use of reactivity indexes. The pyrano[2,3-c]pyrrolidine moiety could be modified, for example by a ring-opening transformation under the action of hydrazine to provide pyrazolyl-substituted pyrrolidines.

Concise Synthesis of Tryptanthrin Spiro Analogues with In Vitro Antitumor Activity Based on One-Pot, Three-Component 1,3-Dipolar Cycloaddition of Azomethine Ylides to Сyclopropenes

Synthesis ◽  
2018 ◽  
Vol 51 (03) ◽  
pp. 713-729 ◽  
Author(s):  
Vitali Boitsov ◽  
Alexander Stepakov ◽  
Alexander Filatov ◽  
Nickolay Knyazev ◽  
Stanislav Shmakov ◽  
...  
Keyword(s):  
Antitumor Activity ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
One Pot ◽  
Economic Method ◽  
Reaction Proceeds ◽  
High Yields

A simple, efficient and atom-economic method has been developed for the synthesis of complex alkaloid-like compounds with spiro-fused indolo[2,1-b]quinazoline and cyclopropa[a]pyrrolizine or 3-azabicyclo[3.1.0]hexane moieties. We have found that one-pot, three-component 1,3-dipolar cycloaddition reactions allow the desired products to be obtained from various cyclopropene derivatives with tryptanthrin-derived azomethine ylides generated in situ, in good to high yields and excellent diastereoselectivity. The possibility of ylide generation was exemplified by using α-amino acids (l-proline, l-4-thiazolidincarboxylic acid) and simplest peptides (dipeptide Gly-Gly, tripeptide Gly-Gly-Gly). Quantum chemical investigations indicate that the reaction proceeds through the S-shaped azomethine ylide, the interaction of which with cyclopropenes proceeds via a less sterically hindered endo-transition state. The antitumor activity of some of spiro-tryptanthrin derivatives against erythroleukemia (K562), cervical carcinoma (HeLa) and colon carcinoma (CT26) cell lines was evaluated in vitro by MTS-assay.

scholarly journals Isolation and characterisation of a stable 2-azaphenalenyl azomethine ylide

2019 ◽  
Vol 2 (1) ◽  
Author(s):  
Koji Katayama ◽  
Akihito Konishi ◽  
Koki Horii ◽  
Makoto Yasuda ◽  
Chitoshi Kitamura ◽  
...  
Keyword(s):  
Azomethine Ylides ◽  
Structural Deformation ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
X Ray ◽  
Isolation And Characterization ◽  
Bond Alternation ◽  
Structural And Electronic Properties ◽  
Deep Green

AbstractAlthough azomethine ylides have been fully exploited as versatile reactive intermediates in dipolar cycloaddition reactions to construct a variety of heterocyclic compounds involving a nitrogen atom, little is known about their structural and electronic properties. Here a method is developed for the preparation, isolation and characterization of a stable 2-azaphenalenyl based azomethine ylide. N-Phenyl-5,8-di-t-butyl-2-azaphenalenyl cannot be isolated because it undergoes rapid dimerization by C–C bond formation at the 1 and 3 positions. In contrast, sterically bulkier N-2,6-di(isopropyl)phenyl-5,8-di-t-butyl-2-azaphenalenyl can be generated and isolated as deep green crystals under deoxygenated conditions. X-ray crystal analysis of this stable azomethine ylide reveals that its azaphenalenyl skeleton has very small bond alternation and structural deformation. The results of spectroscopic and electrochemical theoretical studies indicate that N-2,6-di(isopropyl)phenyl-5,8-di-t-butyl-2-azaphenalenyl has electronic features that are similar to those of phenalenyl anion and it possesses an extremely high HOMO energy.

Azomethine Ylide Cycloaddition of 1,3- dienyl esters: Highly regio- and diastereoselective synthesis of functionalized pyrrolidinochromenes

2022 ◽  
Author(s):  
Manickam Bakthadoss ◽  
Mohammad Mushaf ◽  
Vishal Agarwal ◽  
Tadiparthi Thirupathi Reddy ◽  
Duddu Savaraiah Sharada
Keyword(s):  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Diastereoselective Synthesis

An efficient protocol for the synthesis of tricyclic pyrolidinochromenes has been developed via an intramolecular 1,3-dipolar cycloaddition of azomethine ylides generated in situ from 1,3- dienyl ester tethered O-hydroxyarylaldehyde and...

1,3-Dipolar cycloaddition reactions of phthalic anhydrides with an azomethine ylide

2015 ◽  
Vol 2 (6) ◽  
pp. 705-712 ◽  
Author(s):  
Hugo Santos ◽  
Amy Distiller ◽  
Asha M. D'Souza ◽  
Quentin Arnoux ◽  
Jonathan M. White ◽  
...  
Keyword(s):  
Ring Opening ◽  
Cycloaddition Reaction ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
Ring Opening Reaction ◽  
Phthalic Anhydrides

A series of phthalic anhydrides underwent a 1,3-dipolar cycloaddition reaction with N-benzylazomethine ylide to produce unstable spiro(isobenzofuran-1,5′-oxazolidin)-3-ones, which underwent a subsequent reductive ring-opening reaction to afford 1(3H)-isobenzofuranones.

Recent Advances in the Synthesis of Hetero- and Carbocyclic Compounds­ and Complexes Based on Acenaphthylene-1,2-dione

Synthesis ◽  
2018 ◽  
Vol 50 (20) ◽  
pp. 3947-3973 ◽  
Author(s):  
Issa Yavari ◽  
Aliyeh Khajeh-Khezri
Keyword(s):  
Ring Opening ◽  
Multicomponent Reactions ◽  
Spiro Compounds ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Ring Enlargement ◽  
Recent Advances ◽  
Carbocyclic Compounds ◽  
Wide Range ◽  
Acidic Compounds

Acenaphthylene-1,2-dione has been utilized in a wide range of reactions as a starting material for the synthesis of hetero- and carbocyclic compounds and complexes. This review provides a short summary of the recent advances in the application of acenaphthylene-1,2-dione in the synthesis of hetero- and carbocyclic systems and bioactive compounds. In addition, the applications of acenaphthylene-1,2-dione in the synthesis of spiro compounds, propellanes, and ligands in catalyst reactions, from 2002 to early 2018, are included.1 Introduction2 Synthesis of Spiro Compounds Employing Acenaphthylene-1,2-dione2.1 Methods for the Construction of Spiro Compounds2.1.1 By 1,3-Dipolar Cycloaddition of Acenaphthylene-1,2-dione via Azomethine Ylides2.1.2 By Multicomponent Reactions of Acenaphthylene-1,2-dione with C–H Acidic Compounds2.1.3 By Reaction of Acenaphthylene-1,2-dione with Zwitterionic Intermediates2.1.4 By Substitution and Multicomponent Reactions of Acenaphth- ylene-1,2-dione with Different Nucleophiles3 Synthesis of Propellanes by Employing Acenaphthylene-1,2-dione3.1 Methods for the Construction of Propellanes Based on Acenaph- thylene-1,2-dione3.1.1 By Reaction of Acenaphthylene-1,2-dione with Nucleophiles3.1.2 By Reaction of Acenaphthylene-1,2-dione with Binucleophiles4 Synthesis of Ligands Employing Acenaphthylene-1,2-dione for Catalyst Reactions5 Synthesis of Novel Hetero- and Carbocyclic Compounds Employing Acenaphthylene-1,2-dione5.1 By Reaction of Acenaphthylene-1,2-dione with Nucleophiles5.2 By Reaction of Acenaphthylene-1,2-dione with Zwitterionic Intermediates5.3 By Ring Opening and Ring Enlargement6 Conclusion

scholarly journals Synthesis of pyrrolizidines and indolizidines by multicomponent 1,3-dipolar cycloaddition of azomethine ylides

2019 ◽  
Vol 91 (4) ◽  
pp. 575-596 ◽  
Author(s):  
Carmen Nájera ◽  
José Miguel Sansano
Keyword(s):  
Amino Acid ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Amino Acid Derivatives ◽  
Reaction Conditions ◽  
Dipolar Cycloadditions ◽  
Spiro Derivatives ◽  
Stabilized Azomethine Ylides

Abstract Different multicomponent 1,3-dipolar cycloadditions (1,3-DC) of cyclic α-amino acid derivatives with aldehydes and dipolarophiles have been described as efficient and simple methodologies for the synthesis of the pyrrolidine unit of pyrrolizidines and indolizidines. When free cyclic α-amino acids are used, a thermal promoted decarboxylative process generates in situ the corresponding non-stabilized azomethine ylides, which afforded the corresponding pyrrolizidines and indolizidines with a hydrogen in the bicyclic units. This methodology has been employed to the synthesis of complex systems including spiro derivatives when ketones are used as carbonyl component. In addition, working with cyclic α-amino acid derived esters, the three-component 1,3-DC takes place under milder reaction conditions giving the corresponding pyrrolizidines and indolizidines with an alkoxycarbonyl group in the bridge adjacent carbon to the nitrogen. This methodology can be carried out by a double consecutive or stepwise 1,3-DC to provide pyrrolizidines via the precursor prolinates. The conformation of the azomethine ylide controls the endo/exo diastereoselectivity of the 1,3-DC.

Asymmetric synthesis of polycyclic 3-fluoroalkylproline derivatives by intramolecular azomethine ylide cycloaddition

2019 ◽  
Vol 6 (16) ◽  
pp. 2916-2923 ◽  
Author(s):  
Fernando Rabasa-Alcañiz ◽  
Daniel Hammerl ◽  
Anabel Sánchez-Merino ◽  
Tomás Tejero ◽  
Pedro Merino ◽  
...  
Keyword(s):  
Asymmetric Synthesis ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition

The asymmetric intramolecular dipolar cycloaddition of azomethine ylides was developed for fluorinated dipolarophiles, being the RF group crucial for selectivity.

Comparison of orbital symmetry allowed and forbidden ring opening of aziridines

1978 ◽  
Vol 56 (3) ◽  
pp. 273-288 ◽  
Author(s):  
A. C. Oehlschlager ◽  
A. S. Yim ◽  
M. H. Akhtar
Keyword(s):  
Ring Opening ◽  
Dimethyl Fumarate ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Ring Cleavage ◽  
Orbital Symmetry ◽  
Dipolar Cycloadditions ◽  
Dimethyl Maleate ◽  
Reaction Constant ◽  
Direct Generation

The rates of reactions of N-aryl-cis-2,3-diphenyl aziridines (4a–d) with dimethyl acetylenedicarboxylate (DMAD) are dependent only on aziridine concentration suggesting slow conversion of aziridines to azomethine ylides which subsequently react in 1,3-dipolar cycloadditions to yield Δ3-pyrrolines. The Hammett reaction constant (−0.80) determinee for the N-substituents in the slow ring opening further suggests direct generation of azomethine ylides from these aziridines. The stereochemistry of the cycloaddition products derived from cis-1,2,3-triphenylaziridine with DMAD, maleic anhydride, dimethyl maleate, and dimethyl fumarate is consistent with the conrotatory generation of the ylides followed by their stereospecific cis-cis cycloaddition to the dipolarophiles.Similarly, cycloaddition of 7-aryl-6a,7a-dihydroacenaphtha-[1,2]-aziridines (5a–f) with DMAD yields bicyclic Δ3-pyrrolines and the rate is dependent only on aziridine concentration. This suggests the reaction proceeds via a slow disrotatory cleavage of the aziridine rings producing azomethine ylides which undergo subsequent addition to DMAD. The Hammett reaction constant for the ring opening step is +0.74 suggesting that the transition state for the ring cleavage is electron deficient in the aziridinyl ring but the cycloaddition reactions of 5a with isomeric dipolarophiles as well as several dienes and cycloheptatriene reveal only stereospecific 1,2-cycloadditions expected of an azomethine ylide intermediate.

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