Inverse-electron-demand Diels–Alder reactions of α,β-unsaturated hydrazones with 3-methoxycarbonyl α-pyrones

2018 ◽  
Vol 16 (46) ◽  
pp. 8913-8916 ◽  
Author(s):  
Yoshimitsu Hashimoto ◽  
Ryo Abe ◽  
Nobuyoshi Morita ◽  
Osamu Tamura
Keyword(s):  
Diels Alder ◽  
Inverse Electron Demand ◽  
Electron Withdrawing Group ◽  
Electron Demand ◽  
Bicyclic Lactone

Inverse-electron-demand Diels–Alder reactions of 3-electron-withdrawing group substituted α-pyrones with α,β-unsaturated hydrazones as electron-rich counterparts are catalyzed by Eu(hfc)3 to afford bicyclic lactone cycloadducts.

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>

scholarly journals A click chemistry-based microRNA maturation assay optimized for high-throughput screening

2016 ◽  
Vol 52 (53) ◽  
pp. 8267-8270 ◽  
Author(s):  
Daniel A. Lorenz ◽  
Amanda L. Garner
Keyword(s):  
Click Chemistry ◽  
High Throughput ◽  
High Throughput Screening ◽  
Diels Alder ◽  
Inverse Electron Demand ◽  
Electron Demand

A catalytic enzyme-linked click chemistry assay (cat-ELCCA) for Dicer-catalyzed pre-microRNA maturation was optimized to employ inverse-electron demand Diels–Alder (IEDDA) chemistry affording high-throughput screening capability.

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