Heterograft brush copolymers via romp and triple click reaction strategies involving CuAAC, diels–alder, and nitroxide radical coupling reactions

2012 ◽  
Vol 51 (4) ◽  
pp. 899-907 ◽  
Author(s):  
Nese Cakir ◽  
Merve Yavuzarslan ◽  
Hakan Durmaz ◽  
Gurkan Hizal ◽  
Umit Tunca
Keyword(s):  
Click Reaction ◽  
Nitroxide Radical ◽  
Diels Alder ◽  
Coupling Reactions ◽  
Radical Coupling

Polynorbornene‐ g ‐poly(ethylene oxide) Through the Combination of ROMP and Nitroxide Radical Coupling Reactions

2020 ◽  
Vol 58 (5) ◽  
pp. 645-653 ◽  
Author(s):  
Clémence Nicolas ◽  
Wenhao Zhang ◽  
Émilie Choppé ◽  
Laurent Fontaine ◽  
Véronique Montembault
Keyword(s):  
Ethylene Oxide ◽  
Nitroxide Radical ◽  
Coupling Reactions ◽  
Radical Coupling ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene

Ultrafast and Reversible Multiblock Formation by the SET-Nitroxide Radical Coupling Reaction

2010 ◽  
Vol 63 (8) ◽  
pp. 1227 ◽  
Author(s):  
Jakov Kulis ◽  
Craig A. Bell ◽  
Aaron S. Micallef ◽  
Michael J. Monteiro
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Elevated Temperatures ◽  
Click Reaction ◽  
Coupling Reaction ◽  
Nitroxide Radical ◽  
Self Healing ◽  
Exchange Reactions ◽  
Radical Coupling ◽  
End Groups

The single electron transfer-nitroxide radical coupling (SET-NRC) reaction has been used to produce multiblock polymers with high molecular weights in under 3 min at 50°C by coupling a difunctional telechelic polystyrene (Br-PSTY-Br) with a dinitroxide. The well known combination of dimethyl sulfoxide as solvent and Me6TREN as ligand facilitated the in situ disproportionation of CuIBr to the highly active nascent Cu0 species. This SET reaction allowed polymeric radicals to be rapidly formed from their corresponding halide end-groups. Trapping of these carbon-centred radicals at close to diffusion controlled rates by dinitroxides resulted in high-molecular-weight multiblock polymers. Our results showed that the disproportionation of CuI was critical in obtaining these ultrafast reactions, and confirmed that activation was primarily through Cu0. We took advantage of the reversibility of the NRC reaction at elevated temperatures to decouple the multiblock back to the original PSTY building block through capping the chain-ends with mono-functional nitroxides. These alkoxyamine end-groups were further exchanged with an alkyne mono-functional nitroxide (TEMPO–≡) and ‘clicked’ by a CuI-catalyzed azide/alkyne cycloaddition (CuAAC) reaction with N3–PSTY–N3 to reform the multiblocks. This final ‘click’ reaction, even after the consecutive decoupling and nitroxide-exchange reactions, still produced high-molecular-weight multiblocks efficiently. These SET-NRC reactions would have ideal applications in re-usable plastics and possibly as self-healing materials.

Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr

2010 ◽  
Vol 48 (10) ◽  
pp. 2214-2223 ◽  
Author(s):  
Jakov Kulis ◽  
Craig A. Bell ◽  
Aaron S. Micallef ◽  
Michael J. Monteiro
Keyword(s):  
Kinetic Analysis ◽  
Nitroxide Radical ◽  
Coupling Reactions ◽  
Radical Coupling

Postfunctionalization of polyoxanorbornene backbone through the combination of bromination and nitroxide radical coupling reactions

2015 ◽  
Vol 53 (20) ◽  
pp. 2381-2389 ◽  
Author(s):  
Lale Nur Atici ◽  
Erhan Demirel ◽  
Umit Tunca ◽  
Gurkan Hizal ◽  
Hakan Durmaz
Keyword(s):  
Nitroxide Radical ◽  
Coupling Reactions ◽  
Radical Coupling

scholarly journals Studies on the transannular Diels–Alder reaction of 15-membered macrocyclic trienes containing a trans-trans diene. Part I: Synthesis and isomerization of various model cyclopentadecatrienes

1995 ◽  
Vol 73 (10) ◽  
pp. 1675-1694 ◽  
Author(s):  
Dennis G. Hall ◽  
Renate Müller ◽  
Pierre Deslongchamps
Keyword(s):  
Aqueous Media ◽  
Alder Reaction ◽  
Membered Ring ◽  
Diels Alder ◽  
Coupling Reactions ◽  
Diels Alder Reaction ◽  
Trans Diene

The transannular Diels–Alder reaction of 15-membered macrocyclic trienes with a trans-trans-cis (TTC) olefin geometry can lead to A.B.C.[6.6.7] tricyclic products of trans-syn-trans (TST) and cis-syn-cis (CSC) stereochemistry whereas the TTT isomers can produce the trans-anti-cis (TAC) and cis-anti-trans (CAT) tricycles. In order to study the influence of the position (pro-6.6 or pro-6.7) and the nature (alkyl, alkoxymethyl, or formyl) of the dienophile substituent, a set of 10 model cyclopentadecatrienes was prepared. The synthesis of appropriately functionalized trisubstituted dienophile and diene synthons, as well as their coupling reactions affording acyclic precursors, is described in this paper (first in a series of two). A mild and efficient macrocyclization protocol yielded the required methyl- or alkoxymethyl-substituted cyclic substrates. Further transformations led to the formyl-substituted ones. In particular, the TTT macrocycles containing an enal as a dienophile could be completely isomerized to the corresponding TTC thermodynamic isomers in acidic aqueous media. Keywords: transannular, Diels–Alder, 15-membered ring, A.B.C.[6.6.7] tricycles, diterpene.

Room-Temperature, Water-Promoted, Radical-Coupling Reactions of Phenols with tert-Butyl Nitrite

Synlett ◽  
2017 ◽  
Vol 28 (16) ◽  
pp. 2153-2156 ◽  
Author(s):  
Wen-Ting Wei ◽  
Hongze Liang ◽  
Wen-Ming Zhu ◽  
Weida Liang ◽  
Yi Wu ◽  
...  
Keyword(s):  
Room Temperature ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Phenol Derivative ◽  
Tert Butyl ◽  
Radical Coupling ◽  
Air Atmosphere ◽  
Cross Coupling Reaction ◽  
Temperature Water

A radical–radical cross-coupling reaction of phenols with tert-butyl nitrite has been developed with the use of water as an additive. This method allows the construction of C–N bonds under an air atmosphere at room temperature, providing the ortho-nitrated phenol derivative in moderate to good yields.

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