Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(4), P. 1364 - 1416

Published: Jan. 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.

Language: Английский

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Isomerized Green Solid Additive Engineering for Thermally Stable and Eco‐Friendly All‐Polymer Solar Cells with Approaching 19% Efficiency

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(49)

Published: Oct. 12, 2023

Laboratory-scale all-polymer solar cells (all-PSCs) have exhibited remarkable power conversion efficiencies (PCEs) exceeding 19%. However, the utilization of hazardous solvents and nonvolatile liquid additives poses challenges for eco-friendly commercialization, resulting in trade-off between device efficiency operation stability. Herein, an innovative approach based on isomerized solid additive engineering is proposed, employing volatile dithienothiophene (DTT) isomers to modulate intermolecular interactions facilitate molecular stacking within photoactive layers. Through elucidating underlying principles DTT-induced polymer assembly level, a PCE 18.72% achieved devices processed with environmentally benign solvents, ranking it among highest record values all-PSCs. Significantly, such superiorities DTT-isomerized strategy afford excellent compatibility large-area blade-coating techniques, offering promising pathway industrial-scale manufacturing Moreover, these demonstrate enhanced thermal stability extrapolated T80 lifetime 14 000 h, further bolstering their potential sustainable technological advancement.

Language: Английский

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Easy Isomerization Strategy for Additives Enables High‐Efficiency Organic Solar Cells

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(22)

Published: April 27, 2023

Abstract The morphological features of the active layer has always been an important factor limiting efficiency organic solar cells (OSCs). Although halogen‐based additives capable forming non‐covalent bonds with molecules can effectively adjust morphology layer, inner mechanism positional isomerization on crystallization kinetics bulk heterojunction ignored, which hinders further development this technique. Herein, a new additive‐assisted optimization strategy for high‐efficiency OSCs based three isomeric is proposed, have different sites two bromine substituents benzene ring. results demonstrate that symmetrically structured smallest dipole moment, lowest steric hindrance and most uniformly distributed electrostatic potential, form more suitable interactions acceptor, resulting in reasonable molecular spatial distribution better π–π stacking behavior. For other non‐fullerene systems, additive also shows best effect optimizing aggregation stacking. This work provides guidance screening designing excellent improvement capability expected to profound influence increasing without adopting possessing complex conjugated backbones branched chains.

Language: Английский

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Cyano-functionalized pyrazine: an electron-deficient unit as a solid additive enables binary organic solar cells with 19.67% efficiency

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(10), P. 3365 - 3374

Published: Jan. 1, 2024

A strong electron-deficient unit CNPz as a solid additive was developed in PTQ10/ m -BTP-PhC6 binary organic solar cells. high PCE of 19.67% achieved with significant increase the J SC and FF (81.8%).

Language: Английский

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Quadrupole Moment Induced Morphology Control Via a Highly Volatile Small Molecule in Efficient Organic Solar Cells

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 31(18)

Published: Feb. 24, 2021

Abstract Developing novel solid additives has been regarded as a promising strategy to achieve highly efficient organic solar cells with good stability and reproducibility. Herein, small molecule, 2,2′‐(perfluoro‐1,4‐phenylene)dithiophene (DTBF), designed high volatility strong quadrupole moment, is applied additive implement active layer morphology control in cells. Systematic theory simulations have revealed the charge distribution of DTBF its analog their non‐covalent interaction materials. Benefitting from more vital charge–quadrupole interaction, introduction, volatilization effectively induced regular condensed molecular packing layer, leading enhanced photoelectric properties. Thus, efficiency over 17% obtained DTBF‐processed devices, which higher than that devices. Further application different systems contributed deeper comprehension this type additive. This study highlights facile approach optimizing by finely manipulating moment volatile additives.

Language: Английский

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A Triazole‐Substituted Aryl Iodide with Omnipotent Reactivity in Enantioselective Oxidations

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(4), P. 1479 - 1484

Published: Oct. 10, 2019

Abstract A widely applicable triazole‐substituted chiral aryl iodide is described as catalyst for enantioselective oxidation reactions. The introduction of a substituent in ortho‐position to the key its high reactivity and selectivity. Besides robust modular synthesis, main advantage this excellent performance plethora mechanistically diverse transformations, such spirocyclizations, phenol dearomatizations, α‐oxygenations, oxidative rearrangements. DFT‐calculations situ generated [hydroxy(tosyloxy)iodo]arene isomers give an initial rational observed reactivity.

Language: Английский

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Asymmetric Direct/Stepwise Dearomatization Reactions Involving Hypervalent Iodine Reagents

Chemistry - An Asian Journal, Journal Year: 2021, Volume and Issue: 17(4)

Published: Nov. 24, 2021

A remarkable growth in hypervalent iodine-mediated oxidative transformations as stoichiometric reagents well catalysts has been well-documented due to their excellent properties, such mildness, easy handling, high selectivity, environmentally friendly nature, and stability. This review aims at highlighting the asymmetric dearomatization reactions involving iodine compounds. The present article summarizes intra- intermolecular using chiral reagents/catalysts followed by desymmetrization.

Language: Английский

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Catalyst-Substrate Helical Character Matching Determines the Enantioselectivity in the Ishihara-Type Iodoarenes Catalyzed Asymmetric Kita-Dearomative Spirolactonization

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7301 - 7312

Published: March 20, 2023

Catalyst design has traditionally focused on rigid structural elements to prevent conformational flexibility. Ishihara's elegant of conformationally flexible C2-symmetric iodoarenes, a new class privileged organocatalysts, for the catalytic asymmetric dearomatization (CADA) naphthols is notable exception. Despite widespread use Ishihara catalysts CADAs, reaction mechanism remains subject debate, and mode induction not been well established. Here, we report an in-depth computational investigation three possible mechanisms in literature. Our results, however, reveal that this best rationalized by fourth called "proton-transfer-coupled-dearomatization (PTCD)", which predicted be strongly favored over other competing pathways. The PTCD consistent with control experiment further validated applying it rationalize enantioselectivities. Oxidation I(I) catalyst active I(III) species induces defined helical chiral environment delicate balance between flexibility rigidity. A match/mismatch effect substrate's shape transition states was observed. match allows adapt its conformation maximize attractive noncovalent interactions, including I(III)···O halogen bond, N-H···O hydrogen π···π stacking, stabilize state. stereochemical model capable rationalizing variation enantioselectivities developed. present study enriches our understanding how achieve high stereoinduction may serve as inspiration future exploration designs.

Language: Английский

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Chemo-, regio- and enantioselective dearomative (3+2) reaction of non-functionalized 1-naphthols

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(2), P. 386 - 399

Published: Jan. 21, 2022

Language: Английский

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Synthesis of Diastereomeric Hydrobenzofurans and Hydronaphthofurans via an Iodine Reagent-Promoted Intramolecular Dearomatization Reaction

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

The first metal- and base-free construction of diastereomeric hydrobenzofurans hydronaphthofurans, which were capable further transformations to achieve natural product frameworks, was achieved by the intramolecular oxidized dearomatization phenol or naphthol derivatives via promotion iodine reagents. Enantioselective products obtained through chiral substrates catalysts. This step-economical protocol built multiple centers with extensive tolerance various substrates, resulted in a potential molecular library for developing functional polycyclic scaffolds.

Language: Английский

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