A fruitful century for the scalable synthesis and reactions of biphenyl derivatives: applications and biological aspects

Ali, H.A.M.; Ismail, Mohamed A.; Fouda, Abd El‐Aziz S.; Ghaith, Eslam A.

doi:10.1039/d3ra03531j

“…A novel mono cationic biphenyl carboxamidine derivatives 4a – d (Scheme 1 ) were prepared through subsequence steps. Firstly, Suzuki-Miyaura coupling reaction (SMC) of bromobenzonitrile derivatives with substituted phenylboronic acids 2a–c in the presence of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh 3 ) 4 ) as a strong electron-donating and sterically bulky catalyst/ligand afforded biphenylnitriles 3a – d in acceptable yield (69–82%) [ 29 ]. Secondly, compounds 3a – d were converted to the corresponding free bases of biphenyl carboxamidines 4a – d , on treatment with LiN(TMS) 2 followed by hydrolysis with hydrogen chloride/EtOH solution.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of inventive biphenyl and azabiphenyl derivatives as potential insecticidal agents against the cotton leafworm, Spodoptera littoralis

Ghaith,

Ali,

Ismail

et al. 2023

BMC Chemistry

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The emergence of pest resistance of Spodoptera littoralis (order; Lepidoptera, family; Noctuidae) towards the large scale of different classes of insecticides necessitates the development of some new poly-functionalized biphenyl and azabiphenyl with highly anticipated insecticidal bioresponse. Four new biphenyl carboxamidines 4a–d and four aza-analogue picolinamidine derivatives 8a–d were designed and prepared via the treatment of their corresponding carbonitriles with lithium-bis trimethylsilylamide [LiN(TMS)2], followed by hydrolysis with hydrogen chloride. Furthermore, these compounds were elucidated by spectral data, and their toxicity and insecticidal activity were screened against Spodoptera littoralis. Whereby, toxicological and biochemical aspects of the inventively synthesized biphenyl and azabiphenyl derivatives against the cotton leafworm, Spodoptera littoralis were inspected. As regards the indomitable LC50 and LC90 values, biphenyl and aza-analogues 8d, 8a, 4b, and 8b, revealed the furthermost forceful toxic effects with LC50 values of 113.860, 146.265, 216.624, and 289.879 ppm, respectively. Whereby, their LC90 values are 1235.108, 1679.044, 2656.296, and 3381.256 ppm, respectively, and toxicity index being 22.31%, 17.36%, 11.72%, and 8.76%, respectively, comparing with the already recommended, methomyl insecticide, lannate 90% SP (LC50, 25.396 and LC90, 57.860 and toxicity index, 100%). Additionally, electrochemical parameters via DFT studies were carried out for demonstrating and elucidation of structure–activity relationship (SAR) according to highly motived compounds, descriptors, and the in vivo insecticidal activities. Graphical Abstract

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“…The biphenol scaffold plays a fundamental role in the world of natural products, where they are essential building blocks of diverse biological molecules. Nature abounds with instances where electron‐rich aromatic moieties, especially phenols and their derivatives, serve as key precursors for various biphenyl products [1–3] . Plant extracts containing phenolic compounds have demonstrated various biological functions including antibacterial, antifungal, and antimicrobial activities [4] .…”

Section: Introductionmentioning

confidence: 99%

Solar‐Light‐Driven Photocatalytic Oxidative Coupling of Phenol Derivatives over Bismuth‐Based Porous Metal Halide Perovskites

Lee,

Kumar,

Tüysüz

2024

Angewandte Chemie

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The selective oxidative coupling of phenol derivatives, involving carbon‐carbon (C‐C) and carbon‐oxygen (C‐O) bond formation, has emerged as a critical approach in the synthesis of natural products. However, achieving precise control over the selectivity in coupling reactions of unsubstituted phenols utilizing solar light as the driving force remains a big challenge. In this study, we report a series of porous Cs3Bi2X9 (X = Cl, Br, I) photocatalysts with tailored bandgaps and compositions engineered for efficient solar‐light‐driven oxidative phenol coupling. Notably, p‐Cs3Bi2Br9 exhibited about 73 % selectivity for C‐C coupling, displaying a high formation rate of 47.3 μmol gcat.−1 h‑1 under solar radiation. Furthermore, this approach enables control of the site‐selectivity for phenol derivatives on Cs3Bi2X9, enhancing C‐C coupling. The distinctive porous structure and appropriate band‐edge positions of Cs3Bi2Br9 facilitated efficient charge separation, and surface interaction/activation of phenolic hydroxyl groups, resulting in the kinetically preferred formation of C‐C over C‐O bond. Mechanistic insights into the reaction pathway, supported by comprehensive control experiments, unveiled the crucial role of interfacial charge transfers and Lewis acid Bi sites in stabilizing phenolic intermediates, thereby directing the regioselectivity of diradical couplings and resulting in the formation of unsymmetrical biphenols.

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“…Nature abounds with instances where electron-rich aromatic moieties, especially phenols and their derivatives, serve as key precursors for various biphenyl products. [1][2][3] Plant extracts containing phenolic compounds have demonstrated various biological functions including antibacterial, antifungal, and antimicrobial activities. [4] The transformative process, involving the selective oxidative coupling of phenols and the formation of carbon-carbon (CÀ C) and carbon-oxygen (CÀ O) bonds, represents a pivotal step in the synthetic pathways of natural products.…”

Section: Introductionmentioning

confidence: 99%

Solar‐Light‐Driven Photocatalytic Oxidative Coupling of Phenol Derivatives over Bismuth‐Based Porous Metal Halide Perovskites

Lee,

Kumar,

Tüysüz

2024

Angew Chem Int Ed

2

0

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The selective oxidative coupling of phenol derivatives, involving carbon‐carbon (C‐C) and carbon‐oxygen (C‐O) bond formation, has emerged as a critical approach in the synthesis of natural products. However, achieving precise control over the selectivity in coupling reactions of unsubstituted phenols utilizing solar light as the driving force remains a big challenge. In this study, we report a series of porous Cs3Bi2X9 (X = Cl, Br, I) photocatalysts with tailored bandgaps and compositions engineered for efficient solar‐light‐driven oxidative phenol coupling. Notably, p‐Cs3Bi2Br9 exhibited about 73 % selectivity for C‐C coupling, displaying a high formation rate of 47.3 μmol gcat.−1 h‑1 under solar radiation. Furthermore, this approach enables control of the site‐selectivity for phenol derivatives on Cs3Bi2X9, enhancing C‐C coupling. The distinctive porous structure and appropriate band‐edge positions of Cs3Bi2Br9 facilitated efficient charge separation, and surface interaction/activation of phenolic hydroxyl groups, resulting in the kinetically preferred formation of C‐C over C‐O bond. Mechanistic insights into the reaction pathway, supported by comprehensive control experiments, unveiled the crucial role of interfacial charge transfers and Lewis acid Bi sites in stabilizing phenolic intermediates, thereby directing the regioselectivity of diradical couplings and resulting in the formation of unsymmetrical biphenols.

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A fruitful century for the scalable synthesis and reactions of biphenyl derivatives: applications and biological aspects

Abstract: This review provides recent developments in the current status and latest synthetic methodologies of biphenyl derivatives.

Cited by 10 publications

References 216 publications

Synthesis of inventive biphenyl and azabiphenyl derivatives as potential insecticidal agents against the cotton leafworm, Spodoptera littoralis

Synthesis of inventive biphenyl and azabiphenyl derivatives as potential insecticidal agents against the cotton leafworm, Spodoptera littoralis

Solar‐Light‐Driven Photocatalytic Oxidative Coupling of Phenol Derivatives over Bismuth‐Based Porous Metal Halide Perovskites

Solar‐Light‐Driven Photocatalytic Oxidative Coupling of Phenol Derivatives over Bismuth‐Based Porous Metal Halide Perovskites

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