Diels−Alder Reactions of Maskedo-Benzoquinones:  New Experimental Findings and a Theoretical Study of the Inverse Electron Demand Case⊥

2004 ◽  
Vol 69 (7) ◽  
pp. 2348-2354 ◽  
Author(s):  
Odón Arjona ◽  
Rocío Medel ◽  
Joaquín Plumet ◽  
Rafael Herrera ◽  
Hugo A. Jiménez-Vázquez ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Diels Alder ◽  
Inverse Electron Demand ◽  
Experimental Findings ◽  
Electron Demand

Étude DFT des réactions de cycloaddition de type Diels–Alder sur le 4-aza-6-nitrobenzofuroxane

2007 ◽  
Vol 85 (5) ◽  
pp. 331-335 ◽  
Author(s):  
Sameh Ayadi ◽  
Manef Abderrabba
Keyword(s):  
Theoretical Study ◽  
Dft Method ◽  
Diels Alder ◽  
Point Of View ◽  
Activation Barriers ◽  
Inverse Electron Demand ◽  
Electron Demand

The purpose of this work is a theoretical study of Diels–Alder reactions between the 4-aza-6-nitrobenzofuroxan 1 with a series of dienophiles 3a–3c. From a thermodynamic and orbital point of view, we discuss the reactivity and the stereoselectivty of these reactions. Activation barriers in the Diels-Alder reactions of compound 1 with a series of dienophiles 3a–3c have been calculated and discussed.Key words: inverse electron demand Diels–Alder (IEDDA), DFT method, 4-aza-6-nitrobenzofuroxane.

Theoretical study of the BINOL–zinc complex-catalyzed asymmetric inverse-electron-demand imino Diels–Alder reaction: mechanism and stereochemistry

RSC Advances ◽  
2015 ◽  
Vol 5 (113) ◽  
pp. 93318-93330 ◽  
Author(s):  
Weiyi Li ◽  
Na Yang ◽  
Yajing Lv
Keyword(s):  
Reaction Mechanism ◽  
Zinc Complex ◽  
Theoretical Study ◽  
Alder Reaction ◽  
Diels Alder ◽  
Inverse Electron Demand ◽  
Diels Alder Reaction ◽  
Electron Demand

The enantioselectivity originates from the hindrance of a BINOL ligand, and the exo-selectivity is achieved by the favored electrophilic/nucleophilic interaction.

Potassium Arylethynyltrifluoroborate as an Unstrained Dienophile for Ultrafast and On Demand Activation of Bioorthogonal IEDDA Reactions

2019 ◽  
Author(s):  
Zijian Guo ◽  
Bruno Oliveira ◽  
Claudio D. Navo ◽  
Pedro M. S. D. Cal ◽  
Francisco Corzana ◽  
...  
Keyword(s):  
Protein Modification ◽  
Cross Reactivity ◽  
Diels Alder ◽  
Inverse Electron Demand ◽  
On Demand ◽  
Strained Alkenes ◽  
Electron Demand

<p>Strained alkenes and alkynes are the predominant dienophiles used in inverse electron-demand Diels-Alder (IEDDA) reactions, however, their instability, cross-reactivity and accessibility are problematic. Unstrained dienophiles, although physiologically stable and synthetically accessible, react with tetrazines significantly slower relative to strained variants. Here we report the development of potassium arylethynyltrifluoroborates as unstrained dienophiles for ultrafast, chemically triggered IEDDA reactions. By varying the substituents on the tetrazine (e.g. pyridyl- to benzyl-substituents), cycloaddition rates can vary from nearly spontaneous (<i>t</i><sub>1/2</sub>≈ 9 s) to no reaction with the unstrained alkyne-BF3 dienophile. The reported system was applied to protein modification and enabled mutually orthogonal labelling of two distinct proteins.</p>

Potassium Arylethynyltrifluoroborate as an Unstrained Dienophile for Ultrafast and On Demand Activation of Bioorthogonal IEDDA Reactions

2019 ◽  
Author(s):  
Zijian Guo ◽  
Bruno Oliveira ◽  
Claudio D. Navo ◽  
Pedro M. S. D. Cal ◽  
Francisco Corzana ◽  
...  
Keyword(s):  
Protein Modification ◽  
Cross Reactivity ◽  
Diels Alder ◽  
Inverse Electron Demand ◽  
On Demand ◽  
Strained Alkenes ◽  
Electron Demand

<p>Strained alkenes and alkynes are the predominant dienophiles used in inverse electron-demand Diels-Alder (IEDDA) reactions, however, their instability, cross-reactivity and accessibility are problematic. Unstrained dienophiles, although physiologically stable and synthetically accessible, react with tetrazines significantly slower relative to strained variants. Here we report the development of potassium arylethynyltrifluoroborates as unstrained dienophiles for ultrafast, chemically triggered IEDDA reactions. By varying the substituents on the tetrazine (e.g. pyridyl- to benzyl-substituents), cycloaddition rates can vary from nearly spontaneous (<i>t</i><sub>1/2</sub>≈ 9 s) to no reaction with the unstrained alkyne-BF3 dienophile. The reported system was applied to protein modification and enabled mutually orthogonal labelling of two distinct proteins.</p>

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