Diels–Alder Reactivities of Strained and Unstrained Cycloalkenes with Normal and Inverse-Electron-Demand Dienes: Activation Barriers and Distortion/Interaction Analysis

2013 ◽  
Vol 135 (41) ◽  
pp. 15642-15649 ◽  
Author(s):  
Fang Liu ◽  
Robert S. Paton ◽  
Seonah Kim ◽  
Yong Liang ◽  
K. N. Houk
Keyword(s):  
Interaction Analysis ◽  
Diels Alder ◽  
Activation Barriers ◽  
Inverse Electron Demand ◽  
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.

REGIOSELECTIVITY OF HETERO DIELS–ALDER REACTIONS BETWEEN 1-AZA-1,3-BUTADIENE DERIVATIVES AND DIMETHYLVINYLAMINE: A THEORETICAL INVESTIGATION

2006 ◽  
Vol 05 (04) ◽  
pp. 707-718 ◽  
Author(s):  
HAFIDA CHEMOURI ◽  
WAFAA BENCHOUK ◽  
SIDI MOHAMED MEKELLECHE
Keyword(s):  
Linear Relationship ◽  
Theoretical Investigation ◽  
Diels Alder ◽  
Maximum Hardness ◽  
Activation Barriers ◽  
Rule Based ◽  
Inverse Electron Demand ◽  
Theoretical Approaches ◽  
Maximum Hardness Principle ◽  
Electron Demand

The regioselectivity of hetero Diels–Alder reactions between 1-aza-1,3-butadiene derivatives and dimethylvinylamine is elucidated by means of several theoretical approaches, namely, the Gazquez–Mendez rule based on the calculation of local softnesses, barrier activation calculations, maximum hardness principle, and the Houk rule based on the FMO theory. The calculations were performed at the B3LYP/6-31G(d) level of theory, and the obtained results are in agreement with available experimental results. Moreover, the present analysis shows that these inverse electron demand polar cycloadditions present a linear relationship between the activation barriers of the favored ortho regio-isomers and the inverse of electrophilicity differences of the reagents.

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>

Sign in / Sign up

Export Citation Format

Share Document