Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

Chemical Reviews, Год журнала: 2023, Номер 123(4), С. 1364 - 1416

Опубликована: Янв. 17, 2023

Hypervalent aryliodoumiums are intensively investigated as arylating agents. They excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions be performed under mild conditions. In past decades, acyclic aryliodoniums widely explored However, unmet need for is improvement of their notoriously low reaction economy because coproduced iodides during often wasted. Cyclic have intrinsic advantage in terms economy, started receive considerable attention due valuable synthetic applications initiate cascade reactions, can enable construction complex structures, including polycycles with potential pharmaceutical functional properties. Here, we summarizing recent advances made research field cyclic aryliodoniums, nascent design aryliodonium species applications. First, general preparation typical diphenyl iodoniums described, followed by heterocyclic monoaryl iodoniums. Then, initiated arylations coupled subsequent domino summarized construct polycycles. Meanwhile, building biaryls axial atropisomers discussed a systematic manner. Finally, very advance employed halogen-bonding organocatalysts described.

Язык: Английский

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Dual Nickel(II)/Mechanoredox Catalysis: Mechanical‐Force‐Driven Aryl‐Amination Reactions Using Ball Milling and Piezoelectric Materials

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(42)

Опубликована: Авг. 28, 2023

Abstract The combination of a nickel(II) catalyst and mechanoredox under ball‐milling conditions promotes mechanical‐force‐driven C−N cross‐coupling reactions. In this nickel(II)/mechanoredox cocatalyst system, the modulation oxidation state nickel center, induced by piezoelectricity, is used to facilitate highly efficient aryl‐amination reaction, which characterized broad substrate scope, an inexpensive catalysts (NiBr 2 BaTiO 3 ), short reaction times, almost negligible quantity solvents. Moreover, can be readily up‐scaled multi‐gram scale, all synthetic operations carried out atmospheric without need for complicated setups. Furthermore, force‐induced system suitable excitation‐energy‐accepting molecules poorly soluble polyaromatic substrates that are incompatible with solution‐based nickel(II)/photoredox cocatalysts.

Язык: Английский

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Mechanically activated solid state radical polymerization and cross‐linking via piezocatalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(20)

Опубликована: Март 15, 2023

Abstract Piezocatalysis offers a means to transduce mechanical energy into chemical potential, harnessing physical force drive redox reactions. Working in the solid state, we show here that piezoelectric BaTiO 3 nanoparticles can load flux of reactive radical species capable initiating state free polymerization. Activation powder by ball milling, striking with hammer, or repeated compressive loading generates highly hydroxyl radicals (⋅OH), which readily initiate chain growth and crosslinking acrylamide, acrylate, methacrylate styrenic monomers. Control experiments indicate critical role for chemisorbed water on nanoparticle surface, is oxidized ⋅OH via mechanoredox catalysis. The force‐induced production compressing dry materials represents promising new route harness synthesis.

Язык: Английский

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Piezoelectrically Mediated Reactions: From Catalytic Reactions to Organic Transformations

Chinese Journal of Chemistry, Год журнала: 2022, Номер 41(1), С. 111 - 128

Опубликована: Сен. 13, 2022

Comprehensive Summary Recently, piezocatalysis has attracted considerable attention as a new type of renewable mechanical energy conversion technology, which relies on the strain induced polarization piezoelectric material. This technology been extensively applied in applications water splitting, remediation, gas purification and tumor therapy. Despite rapid development piezocatalysis, utilization materials for synthetic purpose is still under exploration. Piezoelectric means to promote organic reactions expand scope piezoelectrically mediated show successes both polymer synthesis. Herein, we provide comprehensive review recent progress reactions, catalytic mechanisms last few years. The limitations future directions this area are also discussed. We believe will insights into underlying mechanism electron transfer process guide design chemistry.

Язык: Английский

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Resonant acoustic mixing (RAM) for efficient mechanoredox catalysis without grinding or impact media

Chemical Communications, Год журнала: 2022, Номер 59(8), С. 1010 - 1013

Опубликована: Дек. 12, 2022

Resonant acoustic mixing (RAM) enables mechanoredox catalysis with BaTiO3 as the piezoelectric catalyst on model diazonium coupling reactions. RAM proceeds without formal grinding or impact media, is faster than analogous ball-milling strategy, and readily scalable. X-ray diffraction spectroscopy indicate that reusability of a under might be limited by boration.

Язык: Английский

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CdS nanocages@defective-CoNi-LDH with bilayer porous hollow frameworks toward optimized sono-photocatalytic performance

Journal of Materials Chemistry A, Год журнала: 2022, Номер 10(31), С. 16439 - 16447

Опубликована: Янв. 1, 2022

HCNs@HD-CoNi-LDH are fabricated via Cd-based Prussian blue analog nanocubes twice sulfidation and epitaxial growth ZIF-67 etching into hollow defective CoNi-LDH strategies, which exhibit excellent sono-photocatalytic performance due to special bilayer porous frameworks.

Язык: Английский

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Mechanoredox Catalysis Enables a Sustainable and Versatile Reversible Addition‐Fragmentation Chain Transfer Polymerization Process

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(2)

Опубликована: Ноя. 17, 2022

The sustainable synthesis of macromolecules with control over sequence and molar mass remains a challenge in polymer chemistry. By coupling mechanochemistry electron-transfer processes (i.e., mechanoredox catalysis), an energy-conscious controlled radical polymerization methodology is realized. This work explores efficient reversible addition-fragmentation chain transfer (RAFT) process using mechanical stimuli by implementing piezoelectric barium titanate diaryliodonium initiator minimal solvent usage. RAFT demonstrates exquisite poly(meth)acrylate dispersity length while also showcasing alternative to the solution-state semifluorinated polymers that typically utilize exotic solvents and/or reagents. chemistry will find utility development materials across energy, biomedical, engineering communities.

Язык: Английский

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Tribochemically Controlled Atom Transfer Radical Polymerization Enabled by Contact Electrification

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(37)

Опубликована: Июль 29, 2023

Traditional mechanochemically controlled reversible-deactivation radical polymerization (RDRP) utilizes ultrasound or ball milling to regenerate activators, which induce side reactions because of the high-energy and high-frequency stimuli. Here, we propose a facile approach for tribochemically atom transfer (tribo-ATRP) that relies on contact-electro-catalysis (CEC) between titanium oxide (TiO2 ) particles CuBr2 /tris(2-pyridylmethylamine (TPMA), without any input. Under friction induced by stirring, TiO2 are electrified, continuously reducing /TPMA into CuBr/TPMA, thereby conversing alkyl halides active radicals start ATRP. In addition, effect reaction was elucidated theoretical simulation. The results indicated increasing frequency could reduce energy barrier electron from /TPMA. this study, design tribo-ATRP successfully achieved, enabling CEC (ca. 10 Hz) access variety polymers with predetermined molecular weights, low dispersity, high chain-end fidelity.

Язык: Английский

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Mechanochemically Promoted Functionalization of Postconsumer Poly(Methyl Methacrylate) and Poly(α‐Methylstyrene) for Bulk Depolymerization

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(44)

Опубликована: Июль 15, 2024

We describe a methodology of post-polymerization functionalization to enable subsequent bulk depolymerization monomer by utilizing mechanochemical macro-radical generation. By harnessing ultrasonic chain-scission in the presence N-hydroxyphthalimide methacrylate (PhthMA), we successfully chain-end functionalize polymers promote bulk, achieving up 82 % poly(methyl methacrylate) (PMMA) and poly(α-methylstyrene) (PAMS) within 30 min. This method yields high-purity that can be repolymerized. Moreover, as compared most common methods depolymerization, this work is efficient with ultra-high molecular weight (UHMW) polymers, establishing potential address highly persistent, non-degradable all-carbon backbone plastic materials. Lastly, demonstrate expansion commercial cell cast PMMA, high degrees from post-consumer waste. first demonstration applying PhthMA-promoted strategies homopolymer PMMA PAMS prepared conventional polymerization methods.

Язык: Английский

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Aerobic mechanochemical reversible-deactivation radical polymerization

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 22, 2024

Abstract Polymer materials suffer mechano-oxidative deterioration or degradation in the presence of molecular oxygen and mechanical forces. In contrast, aerobic biological activities combined with stimulus promote tissue regeneration repair various organs. A synthetic approach which energy synergistically initiate polymerization will afford similar robustness polymeric materials. Herein, mechanochemical reversible-deactivation radical was developed by design an organic mechano-labile initiator converts into activators response to ball milling, enabling reaction proceed air low-energy input, operative simplicity, avoidance potentially harmful solvents. addition, this not only complements existing methods access well-defined polymers but also has been successfully employed for controlled (meth)acrylates, styrenic monomers solid acrylamides as well synthesis polymer/perovskite hybrids without solvent at room temperature are inaccessible other means.

Язык: Английский

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