Stereocontrolled cyclization of inherently chiral medium-sized rings DOI Creative Commons
Nicolò Tampellini, Brandon Q. Mercado, Scott J. Miller

et al.

Published: Aug. 29, 2024

Asymmetric catalysis evolved as an elegant, efficient and sustainable approach for the synthesis of a multitude chiral molecules.1 However, imparting high levels stereocontrol in complex forms chirality remains significant challenge, particularly when known synthetic routes to target compounds are very few use harsh conditions. Medium-sized rings which display inherent often exhibit attractive properties drug development;2-5 yet, they suffer from limitations due challenging cyclization steps that form strained ring. In fact, no enantioselective method is inherently seven-membered lack local stereogenic elements. this work, we present organocatalytic strategy construct seven- eight-membered featuring under mild conditions with stereocontrol. Notably, same iminophosphorane catalyst orchestrates substrates two different ring sizes, mechanistic paradigms. Our results provide entry into enantioenriched, congested medium-sized feature configurational stability. We believe relying on control cyclization, could be adapted other ring-forming reactions presently or unattainable. The size versatility generality offer important precedent further study features may enable broad success these concepts broader platforms.

Language: Английский

Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages DOI

Fenglei Qiu,

Xinting Zhang,

Wenjing Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 2, 2025

The development of new chiral building blocks for constructing complex architectures, such as macrocycles and cages, is both crucial challenging. Although concave-shaped calixarenes have been established versatile the synthesis cage compounds, there are no reports on cages constructed from calix[4]arene derivatives. Herein, we present a straightforward effective method gram-scale member macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As proof concept, functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via Duff reaction to construct porous organic (CPOCs) using polyamine synthons. Specifically, employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine tris(4-aminophenyl)amine, assemble with PC[4]ACHO resulting in [2 + 4] lantern-shaped [6 8] truncated octahedral CPOCs, respectively. These structures unambiguously characterized by single-crystal X-ray diffraction circular dichroism (CD) spectroscopy. Notably, CPOCs exhibit internal diameters approximately 3.1 nm, cavity volume around 5300 Å3, high specific surface areas up 1300 m2 g-1 after desolvation, making them among largest reported. Additionally, investigations their sensing performance demonstrate that PC[4]A-based enable enantioselective recognition amino acids This work strongly suggests PC[4]A can serve an excellent block rational design materials practical applications.

Language: Английский

Citations

4
Phase-transfer-catalyst enabled enantioselective C–N coupling to access chiral boron-stereogenic BODIPYs DOI Creative Commons

Xueqing Zhang,

Xiaojuan Lv,

Luying Guo

et al.

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

Published: March 19, 2025

Tetracoordinate boron-based fluorescent materials have shown extensively applications in chemistry, biology and science owing to their unique optoelectronic properties. However, constructing chiral boron-stereogenic fluorophores through practical universal strategies remains rare challenging. Herein, as a proof of concept, we report an enantioselective postfunctionalization boron dipyrromethene dyes (BODIPYs), acess BODIPYs moderate good yields with commendable enantioselectivity. Chiral attracted increasing attention not only distinctively photophysical properties circularly polarized luminescence (CPL) materials, but also diversely structural modification. In this·work, present phase-transfer-catalyst enabled C–N coupling reaction diverse nucleophiles. This method serves SNAr (nucleophilic aromatic substitution reaction) route achieve series amido/amino well demonstrates promising CD and·CPL·activities, excellent biocompatibility, high specificities, showing potential imaging agents. Constructing Here, the authors

Language: Английский

Citations

3
Enantiocontrolled Cyclization to Form Chiral 7- and 8-Membered Rings Unified by the Same Catalyst Operating with Different Mechanisms DOI
Nicolò Tampellini, Brandon Q. Mercado, Scott J. Miller

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Chiral medium-sized rings, albeit displaying attractive properties for drug development, suffer from numerous synthetic challenges due to difficult cyclization steps that must take place form these unusually strained, atropisomeric rings sterically crowded precursors. In fact, catalytic enantioselective methods the formation of chiral seven-membered are unknown, and corresponding eight-membered variants also sparse. this work, we present a substrate preorganization-based, enantioselective, organocatalytic strategy construct seven- featuring chirality is intrinsic ring in absence singular stereogenic atoms or single bond axes chirality. The reactions proceed under mild conditions with high levels stereocontrol. Notably, same bifunctional iminophosphorane catalyst orchestrates substrates two different sizes, mechanistic paradigms. We envision size versatility method could guide further applications asymmetric catalysis other challenging reactions.

Language: Английский

Citations

2
Dynamic Chiral Folding for Arene–Perfluoroarene Force Driven Clamping DOI
Yunying Xu,

Aiyou Hao,

Pengyao Xing

et al.

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

Published: April 20, 2025

Peptide folding provides a feasible protocol to design intelligent chiral supramolecular systems toward sensing, recognition, and many other advanced functions. Here we conjugated dual short peptide arms on the aromatic core in spatially close manner, allowing for intramolecular folding. Through controlling skeleton appended luminophores, efficient chirality transfer terminal pyrenes was realized. The through-space transferred exhibited ultrahigh sensitivity solvent environments. Micropockets within dipeptides would accommodate solvents specifically initiate chiroptical inversion expressed ground-state circular dichroism circularly polarized luminescence at photoexcited states. dynamics also were depicted selective binding of guests through arene-perfluoroarene interactions. We successfully constructed dynamic peptide-based clamp that could control endo- exo-type complexation. This work inspires fabrication materials with adaptability external fields.

Language: Английский

Citations

1
The supramolecular chemistry of monodisperse 1,3,5-triazine oligomers DOI Creative Commons
Luis Escobar, Christopher A. Hunter

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review describes the molecular recognition and self-assembly properties of 1,3,5-triazine-based oligomers different topology: linear, branched, macrocyclic, dendrimeric.

Language: Английский

Citations

0
Organocatalytic Enantioselective Arylation to Access Densely Aryl-Substituted P-Stereogenic Centers DOI
Huilin Hu,

Siqiang Fang,

Xingjie Luo

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Although methods for synthesizing chiral phosphorus scaffolds are available, the potential of this molecular chirality remains largely unexplored. Herein, we present a remote desymmetrization prochiral biaryl phosphine oxides through an organocatalytic asymmetric arylation. This metal-free approach enables efficient synthesis wide range densely functionalized P(V)-stereogenic compounds with good to excellent yields and satisfactory enantioselectivities. Mechanistic studies reveal that hydrogen bonding ion-pairing interactions crucial achieving precise stereocontrol in transformation.

Language: Английский

Citations

2
Advances in Asymmetric Hydrogenation of Unfunctionalized Enol Ethers DOI
Jian Zhang, Yuxi Song, Zhenfeng Zhang

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

Abstract Asymmetric hydrogenation of enol ethers has emerged as a valuable and environmentally friendly method for the preparation optically active cyclic acyclic ethers, some which have demonstrated substantial potential application in synthesis compounds total natural products. Over past few decades, significant attention been devoted to use transition‐metal catalysts, particularly those containing chiral phosphine‐phosphine, phosphine‐amine, or carbene ligands, unfunctionalized ethers. In parallel, frustrated Lewis pair catalysts also successfully applied this transformation, enabling efficient production various This review highlights momentum most notable advances enantioselective (with only alkyl aryl substituents on vinyl group). Owing ubiquitous industrial interest, utility related derivatives is included.

Language: Английский

Citations

0
Stereocontrolled cyclization of inherently chiral medium-sized rings DOI Creative Commons
Nicolò Tampellini, Brandon Q. Mercado, Scott J. Miller

et al.

Published: Aug. 29, 2024

Asymmetric catalysis evolved as an elegant, efficient and sustainable approach for the synthesis of a multitude chiral molecules.1 However, imparting high levels stereocontrol in complex forms chirality remains significant challenge, particularly when known synthetic routes to target compounds are very few use harsh conditions. Medium-sized rings which display inherent often exhibit attractive properties drug development;2-5 yet, they suffer from limitations due challenging cyclization steps that form strained ring. In fact, no enantioselective method is inherently seven-membered lack local stereogenic elements. this work, we present organocatalytic strategy construct seven- eight-membered featuring under mild conditions with stereocontrol. Notably, same iminophosphorane catalyst orchestrates substrates two different ring sizes, mechanistic paradigms. Our results provide entry into enantioenriched, congested medium-sized feature configurational stability. We believe relying on control cyclization, could be adapted other ring-forming reactions presently or unattainable. The size versatility generality offer important precedent further study features may enable broad success these concepts broader platforms.

Language: Английский

Citations

0