Repetitive Two-Step Method for o,o,p- and o,p-Oligophenylene Synthesis through Pd-Catalyzed Cross-Coupling of  Hydroxyterphenylboronic Acid

Yamaguchi, Miyuki; Kimura, Takeshi; Shinohara, Naomi; Manabe, Kei

doi:10.3390/molecules181215207

Cited by 4 publications

(3 citation statements)

References 34 publications

(36 reference statements)

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“…Although largely (but not entirely − ) ignored until 2010, ortho -phenylenes have recently been shown to fold into well-defined helices in solution, with offset stacking between every third arene repeat unit. − They are a simple, fundamental type of polyphenylene, a class which now includes functional polymers, − helical oligomers and polymers, − macrocycles, − and dendrimers . Understanding the folding of o -phenylenes is therefore important not only for their own development as foldamers − but also as models for the conformational behavior of other sterically congested polyphenylenes. − They are also beginning to be used in a variety of applications. For example, Fukushima and Aida have proposed that their folding could be exploited in chiroptical memory elements and have demonstrated their use as alignment layers for discotic liquid crystals .…”

Section: Introductionmentioning

confidence: 99%

Enhanced Helical Folding of ortho-Phenylenes through the Control of Aromatic Stacking Interactions

et al. 2014

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The ortho-phenylenes are a simple class of foldamers, with the formation of helices driven by offset aromatic stacking interactions parallel to the helical axis. For the majority of reported o-phenylene oligomers, the perfectly folded conformer comprises perhaps 50-75% of the total population. Given the hundreds or thousands of possible conformers for even short oligomers, this distribution represents a substantial bias toward the folded state. However, "next-generation" o-phenylenes with better folding properties are needed if these structures are to be exploited as functional units within more complex architectures. Here, we report several new series of o-phenylene oligomers, varying both the nature and orientation of the substituents on every repeat unit. The conformational behavior was probed using a combination of NMR spectroscopy, DFT calculations, and X-ray crystallography. We find that increasing the electron-withdrawing character of the substituents gives oligomers with substantially improved folding properties. With moderately electron-withdrawing groups (acetoxy), we observe >90% of the perfectly folded conformer, and stronger electron withdrawing groups (triflate, cyano) give oligomers for which misfolded states are undetectable by NMR. The folding of these oligomers is only weakly solvent-dependent. General guidelines for the assessment of o-phenylene folding by NMR and UV-vis spectroscopy are also discussed.

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Section: Introductionmentioning

confidence: 99%

Enhanced Helical Folding of ortho-Phenylenes through the Control of Aromatic Stacking Interactions

et al. 2014

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“…Boronic acids and, to a lesser extent, boronate esters as coupling partners in Suzuki–Miyaura reaction have been extensively utilized. However, for preparing higher oligoarenes with multiple valuable groups, the purification and characterization of products have been problematic and remain challenging tasks . As depicted on the following Scheme (Scheme ), the boronic esters 13 and 20 were readily prepared by reacting both the bromoarenes 6 and 19 , separately, with B 2 pin 2 2 .…”

Section: Resultsmentioning

confidence: 99%

Diverse Multi‐Functionalized Oligoarenes and Heteroarenes for Porous Crystalline Materials

et al. 2018

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A modular synthesis of multi‐functionalized biphenyl, terphenyl and higher linear oligophenylene dicarboxylic acids and pyridine‐terminated oligoarenes by stepwise palladium–catalyzed borylation/Suzuki–Miyaura cross‐coupling reactions is described. The presence of several distinct functional groups such as azide, hydroxy, and alkyne, as well as coordinative functional end groups (carboxylic acid or pyridine) combined in a single oligoarene molecular unit at strategic positions offer an advantageous dual‐utility. First, these compounds can serve as useful molecular bricks (ditopic organic linkers) in the construction of complex porous crystalline materials. Second, after the assembly into the crystalline coordination networks, orthogonal functional sites within the linker‐backbone offer tremendous potential from application perspectives as they can be modified by a wide range of post‐synthetic modifications including azide–alkyne click chemistry. This allows further tailoring of the supramolecular assemblies to yield novel multifunctional materials.

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“…These motifs are used in many applications, such as pharmaceutical compounds, [8][9][10][11][12] catalysts, [13][14][15] and foldamers. [16][17][18][19] To date, various synthetic methods have been used to synthesize ortho-teraryls. [20][21][22][23] In 1997, Miura and colleagues reported Pd-catalyzed C-H arylation of [1,1′-biphenyl]-2-ol with haloarenes, yielding 2′-arylated compounds.…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed C–H Arylation of [1,1′-Biphenyl]-2-ols with Chloroarenes

Kinoshita

Yamaguchi

Sasou

et al. 2023

CHEMICAL & PHARMACEUTICAL BULLETIN

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Palladium-catalyzed, hydroxy-group-directed C-H arylation of [1,1′-biphenyl]-2-ols with chloroarenes was performed. The reaction showed a broad substrate scope and was successfully applied to pharmaceuticals containing a chloro group. Using 2-heteroarylphenols instead of [1,1′-biphenyl]-2-ols also yielded the desired products. The arylated product was further transformed into a triphenylene derivative.

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Repetitive Two-Step Method for o,o,p- and o,p-Oligophenylene Synthesis through Pd-Catalyzed Cross-Coupling of Hydroxyterphenylboronic Acid

Cited by 4 publications

References 34 publications

Enhanced Helical Folding of ortho-Phenylenes through the Control of Aromatic Stacking Interactions

Enhanced Helical Folding of ortho-Phenylenes through the Control of Aromatic Stacking Interactions

Diverse Multi‐Functionalized Oligoarenes and Heteroarenes for Porous Crystalline Materials

Palladium-Catalyzed C–H Arylation of [1,1′-Biphenyl]-2-ols with Chloroarenes

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