Enantioselective construction of inherently chiral pillar[5]arenes via palladium-catalysed Suzuki–Miyaura cross-coupling

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 10, 2025

Pillar[n]arenes have broad applications in biological medicine, materials science, and supramolecular gels. Notably, enantiopure pillar[5]arenes are valued for their roles enantioselective host–guest recognition, chiral sensing, asymmetric catalysis, related fields. Current methods obtaining pillar[n]arenes rely heavily on resolution agents or HPLC resolution. However, the synthesis of these compounds via catalysis remains challenging. In this study, we develop an extended side-arm Suzuki–Miyaura cross-coupling strategy to construct inherently with excellent yields high enantioselectivities using a palladium catalyst Sadphos ligand. The reaction scope extends beyond arylboronic acids encompass 2-arylvinylboronic other multi-OTf-substituted substrates, all efficiently producing desired products. Further exploration synthetic applications, along photophysical chiroptical analyses, confirm potential diverse across multiple disciplines. Enantiopure recognition but current Here, authors pillar[5]arenes.

Language: Английский

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Catalytic Enantioselective Synthesis of Inherently Chiral Calix[4]arenes via Sequential Povarov Reaction and Aromatizations

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 8, 2024

Inherently chiral calix[4]arenes represent a unique type of molecules with significant applications, yet their catalytic enantioselective synthesis remains largely underexplored. We report herein the inherently through sequential organocatalyzed Povarov reaction and aromatizations. The phosphoric acid catalyzed three-component involving amino group-substituted calix[4]arenes, aldehydes (di)enamides desymmetrized prochiral calix[4]arene substrates, which was followed by various aromatization methods, resulting in diverse array novel quinoline-containing good yields high enantioselectivities (up to 75 % yield, 99 ee). large-scale derivatizations products highlight value this method. Furthermore, preliminary exploration into photophysical chiroptical properties demonstrate potential applications these molecules.

Language: Английский

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Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 15, 2024

Inherently chiral calixarenes hold great potential for applications in recognition, sensing, and asymmetric catalysis due to their unique structures. However, special structures relatively large sizes, the catalytic synthesis of inherently is challenging with very limited examples available. Here, we present an efficient method enantioselective sulfur-containing calix[4]arenes through desymmetrizing electrophilic sulfenylation calix[4]arenes. This reaction enabled by a 1,1'-binaphthyl-2,2'-diamine-derived sulfide catalyst hexafluoroisopropanol. Various are obtained moderate excellent yields high enantioselectivities. Control experiments indicate that thermodynamically favored C-SAr product formed from kinetically N-SAr combination hexafluoroisopropanol crucially important both enantioselectivity reactivity. Due authors report

Language: Английский

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Enantioselective Catalytic Synthesis of Inherently Chiral Calixarenes

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Since the introduction of concept inherent chirality by Böhmer, an important part research focused on asymmetric synthesis calixarene macrocycles. However, long synthetic procedures and tedious separation strategies hampered application this technology in many topics organic chemistry, including enantioselective molecular recognition catalysis. Very recently, a new generation catalytic methodologies has been reported, able to provide highly functionalized, inherently chiral calixarenes straightforward manner. In review, we will discuss these methods versatile properties such macrocycles that call for potential applications areas science.

Language: Английский

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Enantioselective Synthesis of Inherently Chiral Pillar[5]Arenes Through Copper‐Catalyzed Azide–Alkyne Cycloaddition

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Pillar[n]arenes have been extensively investigated as carrier materials for applications in host-guest chemistry, nanoscience, information science, and other domains. Despite its success, the enantioselective synthesis of pillar[n]arenes is challenging has not yet achieved. Herein, we present a novel asymmetric extended side-arm strategy synthesizing chiral pillar[5]arenes through an iterative copper-catalyzed azide-alkyne cycloaddition reaction. An increase steric hindrance on both sides macrocyclic molecule efficiently produced wide range high yields with excellent enantioselectivities. Moreover, this principle enables to enantioselectively functionalized different triazoles using one-pot process.

Language: Английский

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Enantioselective Synthesis of Inherently Chiral Pillar[5]Arenes Through Copper‐Catalyzed Azide–Alkyne Cycloaddition

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract Pillar[n]arenes have been extensively investigated as carrier materials for applications in host‐guest chemistry, nanoscience, information science, and other domains. Despite its success, the enantioselective synthesis of pillar[n]arenes is challenging has not yet achieved. Herein, a novel asymmetric extended side‐arm strategy presented synthesizing chiral pillar[5]arenes through an iterative copper‐catalyzed azide–alkyne cycloaddition reaction. An increase steric hindrance on both sides macrocyclic molecule efficiently produced wide range high yields with excellent enantioselectivities. Moreover, this principle enables to enantioselectively functionalized different triazoles using one‐pot process.

Language: Английский

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C₄-Symmetric Inherently Chiral Macrocycles from Organocatalytic Enantioselective Desymmetrization of Resorcin[4]arenes

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6018 - 6024

Published: March 28, 2025

Language: Английский

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Synthesis of Inherently Chiral Germepins via Rh-Catalyzed Enantioselective C–H Germylation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

A rhodium-catalyzed enantioselective C-H germylation reaction was developed, enabling the synthesis of germepin derivatives with diverse substitutions. This study represents a rare application E-H/C-H (E = Si or Ge) dehydrogenation coupling reactions in synthesizing inherently chiral molecules, marking first successful seven-membered heterocycles containing group 14 elements. Compared to their structurally analogous tribenzosilepins, tribenzogermepins exhibit enhanced stereochemical stability under conditions. Furthermore, compatibility Si-H bond identical conditions highlights distinct reactivity and Ge-H bonds.

Language: Английский

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Enantioselective Synthesis of Inherently Chiral Tetraazacalix[4]aromatics from a Chiral Phosphoric Acid-Catalyzed Intramolecular S_NAr Reaction

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

Inherently chiral calixarenes and heteracalixaromatics (ICCHeC) have been drawing great attention, because of their unique 3D stereochemical structures tantalizing applications. The majority ICCHeC arises from the cyclic arrays different aromatic segments. Examples generated various substituents on methylene heteroatom linkages are extremely rare. Here, we report enantioselective synthesis tetraazacalix[1]arene[1]pyridine[2]triazines a phosphoric acid-catalyzed SNAr reaction. inherent chirality resulting 1,3-alternate heteracalix[4]aromatics stems variation only one substituent bridging nitrogen atom. Enantiomers were very stable, they did not undergo racemization at an elevated temperature. This study opens new avenue to design construct novel functional that may find useful applications in supramolecular science.

Language: Английский

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Catalytic enantioselective synthesis of inherently chiral calix[4]arenes via organocatalyzed aromatic amination enabled desymmetrization

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 26, 2025

Inherently chiral calix[4]arenes represent a distinct class of frameworks whose chirality arises from the dissymmetry entire molecule. Although these scaffolds have been widely applied in various research fields, their catalytic enantioselective synthesis remains largely underexplored. Herein, we report inherently using an organocatalyzed desymmetrization method. By phosphoric acid catalysis, asymmetric electrophilic amination reactions phenol-containing prochiral led to range with high yields and enantioselectivities. Significantly, practicability this method is underscored by its successful implementation as little 0.05 mol% catalyst, without compromising reaction efficiency enantioselectivity. Moreover, aminophenol moiety products could be easily modified produce unique diverse N,O-heterocycles, well simple meta-amino-substituted calix[4]arene, which shown promising potential development new catalysts.

Language: Английский

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