Preparation of conjugated polyphenylenes from maleimide-based enediynes through thermal-triggered Bergman cyclization polymerization

Sun, Shiyuan; Zhu, Chuanchuan; Song, Depeng; Li, Fēi; Hu, Aiguo

doi:10.1039/c3py00970j

Cited by 37 publications

(39 citation statements)

References 42 publications

(54 reference statements)

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“…The two adjacent carbonyl groups in the maleimide moiety serve to lower the energy barrier of the Bergman cyclization, permitting the reaction to take place at an even lower temperature (130-160 °C) [36]. Scheme 5 Synthetic route for chiral conjugated polymers [35].…”

Section: Methodsmentioning

confidence: 99%

Recent advances of the Bergman cyclization in polymer science

Chen

2015

Sci. China Chem.

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The Bergman cyclization has strongly impacted on a number of fields including pharmaceutics, synthetic chemistry, and material science. The diradical intermediates stemmed from enediynes can not only cause DNA cleavage under physiological conditions but also function as monomer or initiator participants in polymer science. The homo-polymerization of enediynes through the Bergman cyclization to fabricate conjugated polymers is a fascinating strategy due to the advantages of facial operation, high efficiency, tailored structure, and catalyst-free operation. Moreover, conjugated polymers generated through the Bergman cyclization show many remarkable properties, such as excellent thermal stability, good solubility, and processability, which enables these polymers to be further manufactured into carbon-rich materials. Recent times have seen extensive efforts devoted to the application of the Bergman cyclization in polymer science and materials chemistry. A variety of synthetic strategies have been developed to fabricate structurally unique materials via the Bergman cyclization, including the fabrication of rod-like polymers with polyester, dendrimers and chiral imide side chains, functionalization of carbon nanomaterials by surface-grafting conjugated polymers, formation of nanoparticles by intramolecular collapse of single polymer chains, and the construction of carbon nanomembranes with different morphologies. Future developments involving the Bergman cyclization in polymer science, probably by altering the reaction mechanism to precisely control the microstructure of polymeric products, are also proposed in this review article.

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Section: Methodsmentioning

confidence: 99%

Recent advances of the Bergman cyclization in polymer science

Chen

2015

Sci. China Chem.

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“…The higher molecular weight fractions could be isolated through repeated centrifugation or dialysis, although the size distributions of the obtained brush polymers were wide in all cases. Chiral conjugated polymers with rigid backbones were also synthesized using a similar process [76,77]. Furthermore, the same group reported for the first example of on-surface formation of one-dimensional polyphenylene chains through Bergman cyclization on Cu(110) by combining high-resolution UHV-STM imaging and DFT calculations (Scheme 20) [78].…”

Section: Bergman Reactionmentioning

confidence: 98%

Application of named reactions in polymer synthesis

Jiang

Feng

et al. 2015

Sci. China Chem.

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In recent years, with the rapid development of polymer science, the application of classical named reactions has transferred from small-molecule compounds to polymers. The versatility of named reactions in terms of monomer selection, solvent environment, reaction temperature, and post-modification permits the synthesis of sophisticated macromolecular structures under conditions where other reaction processes will not operate. In this review, we divided the named reactions employed in polymer-chain synthesis into three types: transition metal-catalyzed cross-coupling reactions, metal-free cross-coupling reactions, and multi-components reactions. Thus, we focused our discussion on the progress in the utilization of these named reactions in polymer synthesis.

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“…[9b,c, 12] Recently,w eh ave demonstrated that the onset temperatureo fa na cyclic enediyne was significantly lowered with the installation of an electron-withdrawingm aleimide moiety at the ene position. [13] We also found that the cycloaromatization activities of the enediyne compounds could be regulated by simply adjusting the functional groups at the alkynet erminii no rder to realize the generation of free diradicals at low temperature. [14] These maleimide-based enediynes showeds trong DNA-cleavage and tumor cell suppression activities.…”

Section: Introductionmentioning

confidence: 97%

“…In the molecular‐level design of highly reactive metalloenediynes, on the other hand, the structure of the enediyne ligand should also be sophisticatedly modulated to enable the cycloaromatization occurring at low temperature . Recently, we have demonstrated that the onset temperature of an acyclic enediyne was significantly lowered with the installation of an electron‐withdrawing maleimide moiety at the ene position . We also found that the cycloaromatization activities of the enediyne compounds could be regulated by simply adjusting the functional groups at the alkyne termini in order to realize the generation of free diradicals at low temperature .…”

Section: Introductionmentioning

confidence: 99%

Coordination‐Accelerated Radical Formation from Acyclic Enediynes for Tumor Cell Suppression

Zhang

Lü

et al. 2019

Chemistry An Asian Journal

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A maleimide‐based acyclic enediyne with salicylaldiminato substituents at the alkyne termini was synthesized, which was further chelated with three kinds of metal‐ions, CuII, ZnII, and MgII, and form metalloenediynes. The cycloaromatization of this thermally inactive enediyne ligand was greatly accelerated through the coordination with metal ions. Specifically, the CuII‐metalloenediyne showed an extremely low onset temperature of 55 °C and underwent spontaneous cycloaromatization at ambient temperature to produce free radicals, followed by generation of reactive oxygen species in the physiological environment. The metalloenediyne exhibited excellent DNA cleavage ability and high cytotoxicity towards HeLa cells, with half‐maximal inhibitory concentration values comparable to many commercial antitumor agents. The combination of the electron‐withdrawing effect of the maleimide moiety at the ene position and metal coordination at the yne termini provides a new inspiration for designing and synthesizing highly efficient enediyne antitumor agents.

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Preparation of conjugated polyphenylenes from maleimide-based enediynes through thermal-triggered Bergman cyclization polymerization

Cited by 37 publications

References 42 publications

Recent advances of the Bergman cyclization in polymer science

Recent advances of the Bergman cyclization in polymer science

Application of named reactions in polymer synthesis

Coordination‐Accelerated Radical Formation from Acyclic Enediynes for Tumor Cell Suppression

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