Polar Diels-Alder Reactions Under Microwave Irradiation Employing Different Heterocyclic Compounds as Electrophiles

2019 ◽  
Vol 16 (6) ◽  
pp. 527-543 ◽  
Author(s):  
Pedro M.E. Mancini ◽  
Carla M. Ormachea ◽  
María N. Kneeteman
Keyword(s):  
Organic Synthesis ◽  
Heterocyclic Compounds ◽  
Ionic Conduction ◽  
Theoretical Calculations ◽  
Cycloaddition Reaction ◽  
Diels Alder ◽  
The Other ◽  
Conventional Heating ◽  
Protic Ionic Liquids ◽  
Solvent Free Conditions

During the last twenty years, our research group has been working with aromatic nitrosubstituted compounds acting as electrophiles in Polar Diels-Alder (P-DA) reactions with different dienes of diverse nucleophilicity. In this type of reaction, after the cycloaddition reaction, the nitrated compounds obtained as the [4+2] cycloadducts suffer cis-extrusion with the loss of nitrous acid and a subsequent aromatization. In this form, the reaction results are irreversible. On the other hand, the microwave-assisted controlled heating become a powerful tool in organic synthesis as it makes the reaction mixture undergo heating by a combination of thermal effects, dipolar polarization and ionic conduction. As the Diels-Alder (D-A) reaction is one of the most important process in organic synthesis, the microwave (MW) irradiation was applied instead of conventional heating, and this resulted in better yields and shorter reaction times. Several substituted heterocyclic compounds were used as electrophiles and different dienes as nucleophiles. Two experimental situations are involved: one in the presence of Protic Ionic Liquids (PILs) as solvent and the other under solvent-free conditions. The analysis is based on experimental data and theoretical calculations.

Microwave-Assisted Tandem Processes for the Synthesis of N-Heterocycles

2009 ◽  
Vol 62 (3) ◽  
pp. 208 ◽  
Author(s):  
Mohammed Abid ◽  
Béla Török ◽  
Xudong Huang
Keyword(s):  
Organic Synthesis ◽  
Heterocyclic Compounds ◽  
Significant Contribution ◽  
Solid Phase Synthesis ◽  
Solid Phase ◽  
Reaction Rates ◽  
Phase Synthesis ◽  
Microwave Assisted ◽  
Solvent Free Conditions ◽  
Reaction Media

Over the years, microwave-assisted organic synthesis (MAOS) became a commonly applied mainstream tool for the synthesis of heterocyclic compounds. The broad range of emerging applications in this field is mainly due to the significant contribution of MAOS to the development of ecofriendly processes. Various transformations have been developed for the synthesis of N-heterocycles under microwave conditions, including fast and selective processes. Tandem reactions involving greener reaction media, solvent-free conditions, and solid-phase synthesis are of exceptional interest in this area. In most transformations, microwave conditions dramatically enhanced reaction rates, as well as provided improved yields. This account highlights the most recent advancements in MAOS-based tandem processes for the synthesis of N-heterocycles.

scholarly journals L-Lactide polymerization by calix[4]arene-titanium (IV) complex using conventional heating and microwave irradiation

e-Polymers ◽  
2010 ◽  
Vol 10 (1) ◽  
Author(s):  
Marco Frediani ◽  
David Sémeril ◽  
Dominique Matt ◽  
Fabio Rizzolo ◽  
Anna Maria Papini ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Microwave Irradiation ◽  
Organic Synthesis ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Polymerization Rate ◽  
The Other ◽  
Conventional Heating ◽  
Microwave Assisted ◽  
Microwave Effect

AbstractSince the first contributions by Gedye and Giguere in 1986, growing attention has been registered on the use of microwave heating in organic synthesis. However still many aspects need to be clarified especially about the so called “microwave effect” and the possible degradation phenomena that may be recognized during polymer synthesis. In this work the complex cone-25,27- dipropyloxy-26,28-dioxo-calix[4]arene titanium (IV) dichloride (1) has been tested for the ring opening polymerization of L-lactide, comparing the effect of conventional heating with a possible microwave assisted strategy. The polymers obtained were fully characterized (NMR, IR, HPLC-SEC, DSC, MALDI-TOF and WAXD analysis). As expected the use of microwave irradiation induced an increase of the polymerization rate. On the other side the use of microwaves resulted in a slight loss of the control over molecular weight and molecular weight distribution if compared with a conventional thermal treatment.

Corrigendum to: Microwave-Assisted Tandem Processes for the Synthesis of N-Heterocycles

2009 ◽  
Vol 62 (4) ◽  
pp. 392
Author(s):  
Mohammed Abid ◽  
Béla Török ◽  
Xudong Huang
Keyword(s):  
Organic Synthesis ◽  
Heterocyclic Compounds ◽  
Significant Contribution ◽  
Solid Phase Synthesis ◽  
Solid Phase ◽  
Reaction Rates ◽  
Phase Synthesis ◽  
Microwave Assisted ◽  
Solvent Free Conditions ◽  
Reaction Media

Over the years, microwave-assisted organic synthesis (MAOS) became a commonly applied mainstream tool for the synthesis of heterocyclic compounds. The broad range of emerging applications in this field is mainly due to the significant contribution of MAOS to the development of ecofriendly processes. Various transformations have been developed for the synthesis of N-heterocycles under microwave conditions, including fast and selective processes. Tandem reactions involving greener reaction media, solvent-free conditions, and solid-phase synthesis are of exceptional interest in this area. In most transformations, microwave conditions dramatically enhanced reaction rates, as well as provided improved yields. This account highlights the most recent advancements in MAOS-based tandem processes for the synthesis of N-heterocycles.

Synthesis and transannular Diels–Alder reaction of a 13-membered macrocyclic triene having a tetrasubstituted enol ether as dienophile

1990 ◽  
Vol 68 (3) ◽  
pp. 404-411 ◽  
Author(s):  
Gervais Bérubé ◽  
Pierre Deslongchamps
Keyword(s):  
Organic Synthesis ◽  
Alder Reaction ◽  
Diels Alder ◽  
The Other ◽  
Enol Ether ◽  
Diels Alder Reaction ◽  
Other Hand ◽  
Tricyclic Compounds

The syntheses of the acyclic triene trans–trans–cis27 and trans–trans–trans31 are described. Macrocyclization and concomitant transannular Diels–Alder reaction were performed with the chloride derivative obtained from the trans–trans–cis triene alcohol 27 yielding a mixture of the tricyclic compounds trans–syn–trans33 and cis–syn–cis34. On the other hand, macrocyclization of the chloride derived from trans–trans–trans triene 31 was not successful. Keywords: transannular process, Diels–Alder reaction, macrocyclic triene, macrocyclization, tricyclic compounds, organic synthesis.

scholarly journals HUISGEN AND HIS ADVENTURES IN A PLAYGROUND OF MECHANISMS AND NOVEL REACTIONS

Química Nova ◽  
2020 ◽  
Author(s):  
Daniel Gonzaga ◽  
Luana Forezi ◽  
Carolina Lima ◽  
Patricia Ferreira ◽  
Fernando Silva ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Heterocyclic Compounds ◽  
Cycloaddition Reaction ◽  
Professor Emeritus ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
University Of Munich ◽  
The University

The death of professor Rolf Huisgen (1920-2020) was announced on March 26th 2020, in the midst of the COVID-19 pandemic. Professor Huisgen was professor emeritus at the University of Munich in Germany, and studied in detail the mechanism of the 1,3-dipolar cycloaddition reaction, significantly expanding its scope. Even though he did not discover this reaction, it was through his studies that it became important in organic synthesis. Indeed, in honor of his work, the reaction became known as Huisgen’s cycloaddition and it has been consolidated as a useful method for the preparation of five-membered heterocyclic compounds. Considering these facts, in this review we provide an overview on the applications of 1,3-dipolar cycloaddition reactions, starting with the seminal examples in the field and further discussing the most recent applications.

scholarly journals Diels–Alder Cycloaddition to the Bay Region of Perylene and Its Derivatives as an Attractive Strategy for PAH Core Expansion: Theoretical and Practical Aspects

Molecules ◽  
2020 ◽  
Vol 25 (22) ◽  
pp. 5373
Author(s):  
Aneta Kurpanik ◽  
Marek Matussek ◽  
Piotr Lodowski ◽  
Grażyna Szafraniec-Gorol ◽  
Michał Krompiec ◽  
...  
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Organic Synthesis ◽  
Aromatic Hydrocarbons ◽  
Theoretical Calculations ◽  
Modern Technology ◽  
Diels Alder ◽  
Point Of View ◽  
Synthetic Method ◽  
Polycyclic Aromatics ◽  
Polycyclic Aromatic

PAHs (polycyclic aromatics hydrocarbons), the compound group that contains perylene and its derivatives, including functionalized ones, have attracted a great deal of interest in many fields of science and modern technology. This review presents all of the research devoted to modifications of PAHs that are realized via the Diels–Alder (DA) cycloaddition of various dienophiles to the bay regions of PAHs, leading to the π-extension of the starting molecule. This type of annulative π-extension (APEX) strategy has emerged as a powerful and efficient synthetic method for the construction of polycyclic aromatic hydrocarbons and their functionalized derivatives, nanographenes, and π-extended fused heteroarenes. Then, [4 + 2] cycloadditions of ethylenic dienophiles, -N=N-, i.e., diazo-dienophiles and acetylenic dienophiles, are presented. This subject is discussed from the organic synthesis point of view but supported by theoretical calculations. The possible applications of DA cycloaddition to PAH bay regions in various science and technology areas, and the prospects for the development of this synthetic method, are also discussed.

scholarly journals Recent applications of intramolecular Diels–Alder reaction in total synthesis of natural products

RSC Advances ◽  
2015 ◽  
Vol 5 (63) ◽  
pp. 50890-50912 ◽  
Author(s):  
Majid M. Heravi ◽  
Vaezeh Fathi Vavsari
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Organic Synthesis ◽  
Cycloaddition Reaction ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Diels–Alder (D–A) reaction is undoubtedly the most powerful [4 + 2] cycloaddition reaction in organic synthesis.

scholarly journals A DFT investigation of Diels-Alder reaction of ethyl propiolate to the cage-annulated hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione

2018 ◽  
Vol 83 (7-8) ◽  
pp. 837-846
Author(s):  
Abdurrahman Atalay ◽  
Riza Abbasoglu
Keyword(s):  
Theoretical Calculations ◽  
Cycloaddition Reaction ◽  
Dft Method ◽  
Alder Reaction ◽  
Diels Alder ◽  
Frontier Molecular Orbital ◽  
Kinetic Control ◽  
Diels Alder Reaction ◽  
Potential Map ◽  
Good Agreement

The Diels?Alder (DA) reaction between the cage-annulated diene hexacyclo[7.5.2.01,6.06,13.08,12.010,14]hexadeca-2,4-diene-7,16-dione (HHDD) with a cyclohexa-1,3-diene moiety and ethyl propiolate (EP) dienophile was investigated by the DFT method at the B3LYP/6-31+G(d,p) level to elucidate the mechanism and regioselectivity features of the reaction. The geometrical and electronic structures of the caged diene HHDD and EP were studied at B3LYP/6-31+G(d,p) level. In order to identify facial- and regio-selectivity of the DA reaction of HHDD and EP, the frontier molecular orbital (FMO) interactions of the reactants according to the FMO theory, and the molecular electrostatic potential map of HHDD were examined. The potential energy surface (PES) of the related DA reaction was calculated, and optimizations of transition states and of products corresponding to critical points on the PES were performed at the B3LYP/6-31+G(d,p), and their configurations were determined. In addition, the thermodynamic and kinetic parameters of each possible cycloaddition reaction were calculated using the B3LYP/6-31+G(d,p) method to determine whether the reaction occurs under thermodynamic or kinetic control. The thermochemical results showed that the related DA cycloaddition proceeds under kinetic control, and the activation energies of syn cycloadditions are clearly lower than that of anti cycloadditions. The theoretical calculations are in good agreement with experimental results.

Ionic Liquids for the Synthesis of Five-Membered N,N-, N,N,N- and N,N,N,NHeterocycles

2019 ◽  
Vol 23 (11) ◽  
pp. 1214-1238 ◽  
Author(s):  
Navjeet Kaur ◽  
Pranshu Bhardwaj ◽  
Meenu Devi ◽  
Yamini Verma ◽  
Neha Ahlawat ◽  
...  
Keyword(s):  
Ionic Liquids ◽  
Organic Synthesis ◽  
Heterocyclic Compounds ◽  
Reaction Medium ◽  
Environmental Issues ◽  
Organic Reaction ◽  
Environment Friendly ◽  
The Past ◽  
Area Of Interest ◽  
Major Subject

Due to special properties of ILs (Ionic Liquids) like their wide liquid range, good solvating ability, negligible vapour pressure, non-inflammability, environment friendly medium, high thermal stability, easy recycling and rate promoters etc. they are used in organic synthesis. The investigation for the replacement of organic solvents in organic synthesis is a growing area of interest due to increasing environmental issues. Therefore, ionic liquids have attracted the attention of chemists and act as a catalyst and reaction medium in organic reaction with high activity. There is no doubt that ionic liquids have become a major subject of study for modern chemistry. In comparison to traditional processes the use of ionic liquids resulted in improved, complimentary or alternative selectivities in organic synthesis. The present manuscript reported the synthesis of multiple nitrogen containing five-membered heterocyclic compounds using ionic liquids. This review covered interesting discoveries in the past few years.

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