Molecular Engineering of Chalcogen‐Embedded Anthanthrenes via<i>peri</i>‐Selective C−H Activation: Fine‐Tuning of Crystal Packing for Organic Field‐Effect Transistors

Liu, Zheng; Han, Wenqiao; Lan, Jingbo; Sun, Lingyan; Tang, Junbin; Zhang, Cheng; You, Jingsong

doi:10.1002/anie.202211412

Cited by 6 publications

(4 citation statements)

References 70 publications

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“…In 2023, we developed a RhCl 3 -catalyzed oxidative Ar−H/ Ar−H homocoupling of 1-(methylthio)naphthalenes to give 8,8′-bis(methylthio)-1,1′-binaphthalenes. 71 Interestingly, employment of the commonly used [Cp*RhCl 2 ] 2 as the precatalyst failed to yield the desired product. This reaction exhibited a wide range of substrate applicabilities and robust functional group tolerance.…”

Section: Development Of Tadf Emitters Formentioning

confidence: 99%

Section: Discovery Of Organic Optoelectronic Materialsmentioning

confidence: 99%

“…Leveraging the intrinsic functionality of the DG, the ortho -C–H-selective (hetero)arylation and subsequent intramolecular C–H cyclization with the DG facilitate the formation of the desired condensed heteroaromatics. This strategy significantly simplifies the synthetic routes for fused heterocycles, including fluorenones, dibenzothiophene 5,5-dioxides, phenanthridines, benzo[ c ]cinnolines, biaryl imides, thioxanthenothioxanthenes and carbazoles, which are highly useful in the assembly of organic semiconductors. ,− Both two-step and one-pot procedures have been demonstrated within this approach. Considering that the reaction conditions for oxidative Ar–H/Ar–H cross-coupling and intramolecular C–H cyclization are generally inconsistent, achieving an optimal one-shot procedure presents challenges, necessitating thorough optimization of reaction conditions.…”

Section: Synthetic Strategies Toward Bi(hetero)aryls and Fused (Heter...mentioning

confidence: 99%

Section: Discovery Of Organic Optoelectronic Materialsmentioning

confidence: 99%

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Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Yang,

Wu,

Bin

et al. 2024

J. Am. Chem. Soc.

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Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are of paramount importance in the quest for organic optoelectronic materials. Among these methods, transition-metalcatalyzed oxidative Ar−H/Ar−H coupling reactions between two (hetero)arenes have emerged as a concise and effective approach for generating a wide array of bi(hetero)aryl and fused heteroaryl structures. This innovative approach bypasses challenges associated with substrate pre-activation processes, thereby allowing for the creation of frameworks that were previously beyond reach using conventional Ar−X/Ar−M coupling reactions. These inherent advantages have ushered in new design patterns for organic optoelectronic molecules that deviate from traditional methods. This ground-breaking approach enables the transcendence of the limitations of repetitive material structures, ultimately leading to the discovery of novel high-performance materials. In this Perspective, we provide an overview of recent advances in the development of organic optoelectronic materials through the utilization of transition-metal-catalyzed oxidative Ar−H/Ar−H coupling reactions. We introduce several notable synthetic strategies in this domain, covering both directed and non-directed oxidative Ar−H/Ar−H coupling strategies, dual chelation-assisted strategy and directed ortho-C−H arylation/cyclization strategy. Additionally, we shed light on the role of oxidative Ar−H/Ar−H coupling reactions in the advancement of high-performance organic optoelectronic materials. Finally, we discuss the current limitations of existing protocols and offer insights into the future prospects for this field.

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Section: Development Of Tadf Emitters Formentioning

confidence: 99%

Section: Discovery Of Organic Optoelectronic Materialsmentioning

confidence: 99%

Section: Synthetic Strategies Toward Bi(hetero)aryls and Fused (Heter...mentioning

confidence: 99%

Section: Discovery Of Organic Optoelectronic Materialsmentioning

confidence: 99%

See 2 more Smart Citations

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Yang,

Wu,

Bin

et al. 2024

J. Am. Chem. Soc.

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Metal‐Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S‐Oxides

Bisht

Popescu

et al. 2023

Angewandte Chemie

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Benzothiophenes, activated by oxidation to the corresponding S-oxides, undergo CÀ H/CÀ H-type coupling with phenols to give C4 arylation products. While an electron-withdrawing group at C3 of the benzothiophene is important, the process operates without a directing group and a metal catalyst, thus rendering it compatible with sensitive functionalitiese.g. halides and formyl groups. Quantum chemical calculations suggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give a π-complex of the corresponding benzothiophene and a phenoxonium cation. Subsequent addition of the phenoxonium cation to the C4 position of the benzothiophene is favored over the addition to C3; Fukui functions predict that the major regioisomer is formed at the more electron-rich position between C3 and C4. Varied selective manipulation of the benzothiophene products showcase the synthetic utility of the metal-free arylation process.

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Metal‐Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S‐Oxides

Bisht

Popescu

et al. 2023

Angew Chem Int Ed

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Benzothiophenes, activated by oxidation to the corresponding S‐oxides, undergo C−H/C−H‐type coupling with phenols to give C4 arylation products. While an electron‐withdrawing group at C3 of the benzothiophene is important, the process operates without a directing group and a metal catalyst, thus rendering it compatible with sensitive functionalities—e.g. halides and formyl groups. Quantum chemical calculations suggest a formal stepwise mechanism involving heterolytic cleavage of an aryloxysulfur species to give a π‐complex of the corresponding benzothiophene and a phenoxonium cation. Subsequent addition of the phenoxonium cation to the C4 position of the benzothiophene is favored over the addition to C3; Fukui functions predict that the major regioisomer is formed at the more electron‐rich position between C3 and C4. Varied selective manipulation of the benzothiophene products showcase the synthetic utility of the metal‐free arylation process.

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Molecular Engineering of Chalcogen‐Embedded Anthanthrenes viaperi‐Selective C−H Activation: Fine‐Tuning of Crystal Packing for Organic Field‐Effect Transistors

Cited by 6 publications

References 70 publications

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Discovery of Organic Optoelectronic Materials Powered by Oxidative Ar–H/Ar–H Coupling

Metal‐Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S‐Oxides

Metal‐Free Arylation of Benzothiophenes at C4 by Activation as their Benzothiophene S‐Oxides

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