Catalytic Enantioselective Access to Planar‐Chiral Macrocyclophanes DOI
Yang Lei, Yanping Zhang, Yong You

et al.

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

Published: May 29, 2025

Macrocyclophanes are a class of macrocyclic molecules featuring aliphatic ansa chains linking non‐adjacent positions an aromatic ring, which have garnered significant attention due to their extensive applications in biological activity, pharmaceutical research, and selective optical recognition. In this review, it summarizes recent advancements the catalytic enantioselective synthesis planar‐chiral macrocyclophanes, focusing on various synthetic routes, including: a) transition‐metal‐catalyzed alkyne cyclotrimerization for planar construction; b) (dynamic) kinetic resolution achiral or prochiral macrocyclophanes; c) substitution rings; d) macrocyclization formation chains. The aim is highlight state‐of‐the‐art advances construction macrocyclophanes push field toward new horizons.

Language: Английский

Enantioselective Synthesis of Pillar[5]arenes by Dynamic Kinetic Resolution via Pd-Catalyzed Suzuki Cross-Coupling DOI

A. Konter,

Jaume Rostoll‐Berenguer, Céline Besnard

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2607 - 2619

Published: Jan. 28, 2025

Language: Английский

Citations

1
Enantioselective Synthesis of Planar/Multiple Chiral [n]Cyclophanes through Asymmetric Allylation DOI Open Access
Ziyang Wang, Xinxin Zhang,

Yidan Sun

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: 43(11), P. 1263 - 1270

Published: March 7, 2025

Comprehensive Summary Planar‐chiral cyclophanes with carbon‐centered chirality are important targets in natural products and pharmaceuticals. However, synthesizing such planar chiral two stereogenic elements via a one‐step asymmetric reaction remains formidable challenge. Herein, we present an efficient kinetic resolution method for planar‐chiral [ n ]cyclophanes chirality. This is achieved through the enantioselective allylation of racemic aldehyde catalyzed by Bi(OAc) 3 phosphoric acid. The delivers multiple high yields excellent enantioselectivities, showcasing remarkable efficiency ( s factor up to 292). broad substrate scope, scalability, potential derivatization highlight value this methodology. DFT calculations have also been performed provide insights into origin experimentally observed diastereo‐ enantioselectivity reaction.

Language: Английский

Citations

1
Enantio-, atrop-, and diastereoselective macrolactonization to access type III cyclophanes DOI Creative Commons
Jiaming Wang, Kang Lv,

Yilu Wen

et al.

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

Published: April 3, 2025

Language: Английский

Citations

1
Conformationally Defined Planar-Chiral [n]Paracyclophanes Stabilized by Chiral Ansa Chains DOI Creative Commons
Changgui Zhao, Jiaming Wang,

Yilu Wen

et al.

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

Abstract Although chiral substituents have been incorporated into ansa chains to stabilize the conformations of cyclophanes and modulate the biological activities pharmaceuticals, asymmetric syntheses these atropisomers relies on substrate-induced diastereoselective macrocyclization. Consequently, enantio-, atrop-, macrocyclizations are yet be reported. Herein, we describe a N-heterocyclic carbene (NHC) phosphoric acid (CPA) dual-catalytic process for desymmetrization 1,3-diols, achieve macrocyclization stereoselective control over two elements. It was deduced that hydrogen bonding CPA with 1,3-diols enhanced diastereoselectivity process. As result, various planar-chiral bearing were synthesized. Thermodynamic experiments revealed presence an all-carbon quaternary carbon center chain significantly increased rotational barriers cyclophanes. Moreover, density functional theory calculations suggested substituent shrinks by compressing bond angle, thereby rendering conformational rotation reaction more challenging.

Language: Английский

Citations

0
Enantioselective Synthesis of Inherently Chiral Pillar[5]Arenes Through Copper‐Catalyzed Azide–Alkyne Cycloaddition DOI Open Access
Wenguang Zhou, Longlong Xi,

Meiru Zhang

et al.

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

Citations

0
Enantioselective Synthesis of Inherently Chiral Pillar[5]Arenes Through Copper‐Catalyzed Azide–Alkyne Cycloaddition DOI Open Access
Wenguang Zhou, Longlong Xi,

Meiru Zhang

et al.

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

Citations

0
Trifluoromethyl Group (CF3) Induced Regioselective Larock Indole Synthesis from Unsymmetric β-CF3-1,3-enynes DOI

Yan‐Hua Qiu,

Peng-Xiang Ma,

Wen‐Hao Shao

et al.

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

Published: March 24, 2025

The indole skeleton exists widely in natural products, pharmaceuticals, and materials. We disclose here a trifluoromethyl group induced regioselective Larock synthetic method from unsymmetric 2-CF3-1,3-enynes. presence of is determinable for the regioselectivity. Once CF3 was replaced with methyl or phenyl group, ratio 1:1 to 1:1.4 isomers were obtained. This strategy features good regioselectivity, broad substrate scope, high functional tolerance. protocol reported offers an alternative solution rare 3,4-functionalization products further transformed show distinctive reactivity hydroboration–oxidation hydro-bromination.

Language: Английский

Citations

0
Synthesis of 12- to 26-Membered Macrocyclic Dienes by Directed Intramolecular Alkene/Alkyne Cross-Coupling DOI

Xiandie Zhang,

Xiuying Liu, Xiaoli Li

et al.

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

Published: April 9, 2025

The first iridium-catalyzed intramolecular alkene/alkyne cross-coupling reaction has been developed to prepare a wide range of 12- 26-membered macrocyclic 1,3-dienes. This operationally simple protocol proceeded by NHTs amide-enabled alkenyl C-H functionalization and exhibited functionality tolerance excellent E/Z ratio selectivity.

Language: Английский

Citations

0
Chiral Amplification and Regulation: Design and Applications of Circularly Polarized Luminescence‐Active Materials Derived From Macrocyclic Compounds DOI Creative Commons
Wei Zhang,

Mao‐Qin Liu,

Yang Luo

et al.

Aggregate, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

ABSTRACT Chirality is a fundamental property in molecules and biological systems, characterized by asymmetric configurational features. Circularly polarized luminescence (CPL) materials have gained significant attention due to their unique optical activities, with applications 3D displays, chiral sensors, catalysis, more. Chiral transfer amplification typically involve the generation of chirality excited state, facilitated interactions like energy transfer, electron or induction. Supramolecular self‐assembly strategies, particularly macrocyclic compounds, enable linking achiral luminescent units through intermolecular interactions. Macrocyclic hosts—cyclodextrins, calix[ n ]arenes, pillar[ cyclophanes, cucurbit[ ]urils—are especially promising stable structures adjustable cavities for guest encapsulation. These compounds induce photophysical properties host–guest complexation, making them ideal constructing amplification, CPL‐active materials. This review summarizes advancements multicolor CPL materials, sensing, induction, separation, highlighting potential supramolecular material design. The challenges future directions this field are also discussed, aiming guide further research application systems.

Language: Английский

Citations

0
Catalytic Enantioselective Access to Planar‐Chiral Macrocyclophanes DOI
Yang Lei, Yanping Zhang, Yong You

et al.

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

Published: May 29, 2025

Macrocyclophanes are a class of macrocyclic molecules featuring aliphatic ansa chains linking non‐adjacent positions an aromatic ring, which have garnered significant attention due to their extensive applications in biological activity, pharmaceutical research, and selective optical recognition. In this review, it summarizes recent advancements the catalytic enantioselective synthesis planar‐chiral macrocyclophanes, focusing on various synthetic routes, including: a) transition‐metal‐catalyzed alkyne cyclotrimerization for planar construction; b) (dynamic) kinetic resolution achiral or prochiral macrocyclophanes; c) substitution rings; d) macrocyclization formation chains. The aim is highlight state‐of‐the‐art advances construction macrocyclophanes push field toward new horizons.

Language: Английский

Citations

0