Stable Aromatic Nitrile Oxides

Macromolecular Surface Design: Photopatterning of Functional Stable Nitrile Oxides

“…[16] The photofragmentation of phenacyls ulfides (i.e., photocaged thioaldehydes) is am ild and efficient method for the preparation of highly reactive thioaldehydes,w hich can be trapped in situ by dienes,n ucleophiles, [17] or in a1 ,3-dipolar cycloaddition with nitronate esters. [20,21] Thec ycloaddition between nitrile oxides and alkynes represents am etal-free ligation reaction that has been employed for polymer end-group modifications. [20,21] Thec ycloaddition between nitrile oxides and alkynes represents am etal-free ligation reaction that has been employed for polymer end-group modifications.…”

“…[18,19] Nitrile oxides are among the most reactive species in organic chemistry and are usually trapped by 1,3-dipolar cycloaddition reactions. [20,21] Thec ycloaddition between nitrile oxides and alkynes represents am etal-free ligation reaction that has been employed for polymer end-group modifications. [22] However,nitrile oxides are prepared in situ from the oxime precursors owing to their rapid dimerization to furoxans,w hich strongly limits their applicability in modular ligation strategies.T he spontaneous dimerization to furoxans can be prevented by substituents on the aromatic ring that is attached to the nitrile oxide group.H owever, employing such stable nitrile oxides in cycloadditions to C=C or C Nm ultiple bonds for polymer modifications requires elevated temperatures.…”

Exploration of Unimolecular and Bimolecular Pathways for Nitrile N‐Oxide Isomerization to Isocyanate Through Global Reaction Route Mapping Techniques

“…On the other hand, a nitrile N ‐oxide, as a reagent for a 1,3‐dipolar cycloaddition reaction, is inactivated by its thermal isomerization to the corresponding isocyanate, and its dimerization to the furoxane, as shown in Scheme . Although a method of suppressing this dimerization reaction has been reported, the issue of inactivation of nitrile N ‐oxides as substrates for click reactions due to isomerization has not been solved.…”

Makromolekulare Oberflächen: Photomusterung mit funktionellen stabilen Nitriloxiden

“…[16] Die Photofragmentierung von Phenacylsulfiden (d. h. photoaktivierbaren Thioaldehyden) ist eine milde und effiziente Methode zur Herstellung hochreaktiver Thioaldehyde,die in situ durch Diene,Nucleophile [17] oder in einer 1,3-dipolaren Cycloaddition mit Nitronatestern [18,19] abgefangen werden kçnnen.Nitriloxide gehçren zu den reaktivsten Spezies in der organischen Chemie und werden gewçhnlich durch 1,3-dipolare Cycloaddition abgefangen. [20,21] Die Cycloaddition zwischen Nitriloxiden und Alkinen ist eine metallfreie Ligationsreaktion, die für die Modifikation von Polymerendgruppenv erwendet wurde. [22] Allerdings werden die Nitriloxide wegen ihrer schnellen Dimerisierung zu Furoxanen in situ aus Oximvorstufen hergestellt, wodurch die Anwendbarkeit in modularen Ligationsstrategien stark eingeschränkt wird.…”

“…Nitriloxide gehçren zu den reaktivsten Spezies in der organischen Chemie und werden gewçhnlich durch 1,3-dipolare Cycloaddition abgefangen. [20,21] Die Cycloaddition zwischen Nitriloxiden und Alkinen ist eine metallfreie Ligationsreaktion, die für die Modifikation von Polymerendgruppenv erwendet wurde. [22] Allerdings werden die Nitriloxide wegen ihrer schnellen Dimerisierung zu Furoxanen in situ aus Oximvorstufen hergestellt, wodurch die Anwendbarkeit in modularen Ligationsstrategien stark eingeschränkt wird.…”