Dynamic Nucleophilic Aromatic Substitution of Tetrazines

A dynamic nucleophilic aromatic substitution of tetrazines (SNTz) is presented herein. It combines all the advantages of dynamic covalent chemistry with the versatility of the tetrazine moiety. Indeed, libraries of compounds or sophisticated molecular structures can be easily obtained, which are sus...

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Bibliographic Details
Published in:Angewandte Chemie 2021-08, Vol.133 (34), p.18931-18939
Main Authors: Santos, Tanausú, Rivero, David S., Pérez‐Pérez, Yaiza, Martín‐Encinas, Endika, Pasán, Jorge, Daranas, Antonio Hernández, Carrillo, Romen
Format: Article
Language:English
Subjects:
Acetylcholine
Aniline
cage compounds
Chemistry
Diels–Alder reaction
Dismantling
dynamic covalent chemistry
Fluorescence
Irradiation
Molecular structure
photolysis
Reagents
Substitution reactions
tetrazine
Thiols
Ultraviolet radiation
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Summary:A dynamic nucleophilic aromatic substitution of tetrazines (SNTz) is presented herein. It combines all the advantages of dynamic covalent chemistry with the versatility of the tetrazine moiety. Indeed, libraries of compounds or sophisticated molecular structures can be easily obtained, which are susceptible to post‐functionalization by inverse electron demand Diels–Alder (IEDDA) reaction, which also locks the exchange. Additionally, the structures obtained can be disassembled upon the application of the right stimulus, either UV irradiation or a suitable chemical reagent. Moreover, SNTz is compatible with the imine chemistry of anilines. The high potential of this methodology has been proved by building two responsive supramolecular systems: A macrocycle that displays a light‐induced release of acetylcholine; and a truncated [4+6] tetrahedral shape‐persistent fluorescent cage, which is disassembled by thiols unless it is post‐stabilized by IEDDA. All the advantages of dynamic covalent chemistry and the versatility of the tetrazine moiety have been combined in a novel exchange reaction: The nucleophilic aromatic substitution of tetrazines (SNTz) with phenols and alkyl thiols. Not only sophisticated structures could be easily synthesized, but more importantly, post‐functionalization by IEDDA or photolysis of the compounds show that SNTz unleashes a huge potential of applications.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202106230