Trienamine catalysis for asymmetric Diels–Alder reactions of 2,4-dienones: a theoretical investigation

2015 ◽  
Vol 13 (22) ◽  
pp. 6313-6324 ◽  
Author(s):  
Zhishan Su ◽  
Chan Kyung Kim
Keyword(s):  
Theoretical Investigation ◽  
Cycloaddition Reaction ◽  
Bifunctional Catalyst ◽  
Diels Alder ◽  
Cinchona Alkaloid

In the Diels–Alder reactions of 2,4-dienones with two dienophiles, cinchona alkaloid acts as an efficient bifunctional catalyst by generating an extended trienamine π-conjugated system and by orienting the dienophile at an appropriate position for a cycloaddition reaction.

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.

Synthese neuer Pyridin-C-nukleoside der 2 ,3 -Didesoxyribose durch „inverse“ [4+2]-Cycloaddition Synthesis of Novel Pyridine-C-nucleosides of 2,3-Dideoxyribose by „Inverse“ [4+2]-Cycloaddition

1997 ◽  
Vol 52 (7) ◽  
pp. 851-858 ◽  
Author(s):  
Gunther Seitz ◽  
Johanna Siegl
Keyword(s):  
Cycloaddition Reaction ◽  
Alder Reaction ◽  
Diels Alder ◽  
The Novel ◽  
Protecting Group ◽  
Enol Ethers ◽  
Inverse Electron Demand ◽  
Diels Alder Reaction ◽  
Cyclic Ketene Acetals

The anomeric imido esters 5 and 6, appropriate precursors for C-nucleoside synthesis, were prepared and utilized as heterodienophiles in a Diels-Alder reaction with inverse electron demand to yield the novel, protected 1.2.4-triazine C-nucleosides 8 and 9. They could be deprotected by treatment with 70% trifluoroacetic acid to furnish the free C-nucleosides 10 and 11. The triazine „aglycon“ of 8 contains an electron deficient diazadiene system, highly activated to react with various electron rich dienophiles such as enamines, enol ethers and several cyclic ketene acetals in an „inverse“ [4+2]-cycloaddition reaction. The Diels-Alder adducts spontaneously eliminate N2 and after follow-up reactions the O-TBDPS protected pyridine-C-nucleosides 13, 15, 17,19, 21 and 23 are formed. Removal of the protecting group by treatment with CF3CO2H /H2O leads to the corresponding 2’,3’-dideoxy-β-D-ribofuranosyl- pyridines.

scholarly journals Furoic Acid and Derivatives as Atypical Dienes in Diels-Alder Reactions

2021 ◽  
Author(s):  
Razvan Cioc ◽  
Tom Smak ◽  
Marc Crockatt ◽  
Jan Kees Van der Waal ◽  
Pieter C A Bruijnincx
Keyword(s):  
Green Chemistry ◽  
Cycloaddition Reaction ◽  
Building Blocks ◽  
Diels Alder ◽  
Furoic Acid

The furan Diels-Alder (DA) cycloaddition reaction has become an important tool in green chemistry, being central to the sustainable synthesis of many chemical building blocks. The restriction to electron-rich furans...

scholarly journals Mechanochemically Gated Photoswitching: Expanding the Scope of Polymer Mechanochromism

Synlett ◽  
2019 ◽  
Vol 30 (15) ◽  
pp. 1725-1732 ◽  
Author(s):  
Ross W. Barber ◽  
Molly E. McFadden ◽  
Xiaoran Hu ◽  
Maxwell J. Robb
Keyword(s):  
Mechanical Activation ◽  
Uv Light ◽  
Cycloaddition Reaction ◽  
Polymeric Materials ◽  
Diels Alder ◽  
Information Storage ◽  
Chemical Transformations ◽  
History Of ◽  
Polymer Mechanochemistry ◽  
Stress Sensing

Mechanophores are molecules that undergo productive, covalent chemical transformations in response to mechanical force. Over the last decade, a variety of mechanochromic mechanophores have been developed that enable the direct visualization of stress in polymers and polymeric materials through changes in color and chemiluminescence. The recent introduction of mechanochemically gated photoswitching extends the repertoire of polymer mechanochromism by decoupling the mechanical activation from the visible response, enabling the mechanical history of polymers to be recorded and read on-demand using light. Here, we discuss advances in mechanochromic mechanophores and present our design of a cyclopentadiene–maleimide Diels–Alder adduct that undergoes a force-induced retro-[4+2] cycloaddition reaction to reveal a latent diarylethene photoswitch. Following mechanical activation, UV light converts the colorless diarylethene molecule into the colored isomer via a 6π-electrocyclic ring-closing reaction. Mechanically gated photoswitching expands on the fruitful developments in mechanochromic polymers and provides a promising platform for further innovation in materials applications including stress sensing, patterning, and information storage.1 Introduction to Polymer Mechanochemistry2 Mechanochromic Reactions for Stress Sensing3 Regiochemical Effects on Mechanophore Activation4 Mechanochemically Gated Photoswitching5 Conclusions

Reactivity of the superhalogen/superalkali ion encapsulated C60 fullerenes

2021 ◽  
Author(s):  
Gibu George ◽  
Anton J Stasyuk ◽  
Miquel Solà
Keyword(s):  
Dft Calculations ◽  
Cycloaddition Reaction ◽  
Diels Alder ◽  
Halogen Species ◽  
C60 Fullerenes

The Diels-Alder cycloaddition reaction between 1,3-cyclohexadiene and a series of C60 fullerenes with encapsulated (super)alkali/(super)halogen species (Li+@C60, Li2F+@C60, Cl-@C60, and LiF2-@C60) was explored by means of DFT calculations. Reactivity of...

One-step Functionalization of Mildly and Strongly Reduced Graphene Oxide with Maleimide: An Experimental and Theoretical Investigation of the Diels-Alder [4+2] Cycloaddition Reaction

2021 ◽  
Author(s):  
Alfonso Ferretti ◽  
Sourab Sinha ◽  
Luca Sagresti ◽  
Esteban Araya-Hermosilla ◽  
Mirko Prato ◽  
...  
Keyword(s):  
Graphene Oxide ◽  
Reduced Graphene Oxide ◽  
Large Scale ◽  
Cycloaddition Reaction ◽  
Diels Alder ◽  
Reduced Form ◽  
Graphene Nanocomposites ◽  
Exfoliated Graphene ◽  
Reduced Graphene ◽  
One Step

For large-scale graphene applications, such as the production of polymer-graphene nanocomposites, exfoliated graphene oxide (GO) and its reduced form (rGO) are presently considered very suitable starting material, showing enhanced chemical...

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