Nickel-Catalyzed Addition of C–C Bonds of Amides to Strained Alkenes: The 1,2-Carboaminocarbonylation Reaction

2022 ◽  
Author(s):  
Yuri Ito ◽  
Syun Nakatani ◽  
Ryota Shiraki ◽  
Takuya Kodama ◽  
Mamoru Tobisu
Keyword(s):  
Strained Alkenes

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>

Palladium-Catalyzed Annulation of Aryl Heterocycles with Strained Alkenes

2007 ◽  
Vol 9 (9) ◽  
pp. 1761-1764 ◽  
Author(s):  
David G. Hulcoop ◽  
Mark Lautens
Keyword(s):  
Palladium Catalyzed ◽  
Strained Alkenes

scholarly journals Diazo group as a new chemical reporter for bioorthogonal labelling of biomolecules

RSC Advances ◽  
2014 ◽  
Vol 4 (94) ◽  
pp. 52241-52244 ◽  
Author(s):  
Laia Josa-Culleré ◽  
Yelena A. Wainman ◽  
Kevin M. Brindle ◽  
Finian J. Leeper
Keyword(s):  
Chemical Reporter ◽  
Strained Alkenes ◽  
Diazo Group

Diazoacetyl groups undergo spontaneous cycloaddition with strained alkenes and alkynes and can be bioorthogonal reporter groups labelling proteins and glycans.

cis-2,3-Di-tert-butylcyclopropanones

1997 ◽  
Vol 75 (7) ◽  
pp. 1030-1040 ◽  
Author(s):  
T.S. Sorensen ◽  
F. Sun
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Carbonyl Group ◽  
Trans Isomer ◽  
Carbonyl Oxygen ◽  
Highly Strained ◽  
Strained Alkenes ◽  
Acyclic Compound

The preparation of the strained cis-2,3-di-tert-butylcyclopropanone 2 from the acyclic compound, α,α′-dibromodineopentyl ketone 1, using a previously reported methodology, is dramatic evidence of both the existence of oxyallyl intermediates in the mechanism of this reaction, and of the integrity with which oxyallyls ring-close to cyclopropanones by a disrotatory route. Because of the bulky cis substituents, cyclopropanone 2 exhibits a number of unusual spectroscopic features (as compared to the trans isomer 5). With the aid of ab initio calculations on 2 and 5, it can be shown that the C2—C3 bond in 2 interacts with the carbonyl π-orbitals, thus causing the carbonyl oxygen to bend 12° out of the plane; this interaction is absent in 5 and the latter has a planar carbonyl group. As with other cyclopropanones, 2 can be photochemically decarbonylated. This process itself appears to be stereospecific even though highly strained alkenes are produced. Cyclopropanone 2 is thermally rearranged to the trans isomer 5 and the kinetics for this are reported; our favoured mechanism involves oxyallyl intermediates. Other reactions of 2 also appear to proceed through these oxyallyl species; for example, alcohols initially add to 2 to give α-alkoxy ends, solutions of 2 enter into very facile diene cycloadditions, and the dimerization of neat 2 also appears to involve these oxyallyl species. Keywords: cyclopropanones, oxyallyl, stereomutation, stereospecific decarbonylation, nonplanar carbonyl.

scholarly journals Isomeric triazines exhibit unique profiles of bioorthogonal reactivity

2019 ◽  
Vol 10 (39) ◽  
pp. 9109-9114 ◽  
Author(s):  
David N. Kamber ◽  
Sean S. Nguyen ◽  
Fang Liu ◽  
Jeffrey S. Briggs ◽  
Hui-Wen Shih ◽  
...  
Keyword(s):  
Unique Reaction ◽  
Strained Alkenes

Isomeric triazines can be tuned to exhibit unique reaction profiles with biocompatible strained alkenes and alkynes.

Rhodium-Catalyzed Tandem Vinylcyclopropanation of Strained Alkenes.

ChemInform ◽  
2006 ◽  
Vol 37 (36) ◽  
Author(s):  
Nai-Wen Tseng ◽  
John Mancuso ◽  
Mark Lautens
Keyword(s):  
Strained Alkenes
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