A stereodynamic probe of Pt(II) molecular hinge for chiroptical sensing of cryptochiral compounds

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

Published: Feb. 25, 2025

Cryptochiral compounds are indispensable in biology systems and medical applications, yet the development of high-performance detection method remains challenging. Here, we report a hinge-like dinuclear Pt(II) complex as stereodynamic probe for cryptochirality sensing. This features constrained, closed conformation achieved through synergistic intramolecular π − stacking metal-metal interactions between cyclometalated wings. The shows robust chiroptical response to center-to-axial chiral induction during rapid condensation with cryptochiral that adopts more energetically favorable conformation. resulting intense Cotton effects at long wavelengths enable in-situ circular dichroism analysis determinate absolute configuration enantiometric composition molecules. Furthermore, near-infrared phosphorescence characteristics hinge have been explored develop it an optical sensor accurate quantification With its dual CD capabilities, this great potential high-throughput screening analysis. authors complexes probes

Language: Английский

---

Dynamic Point-to-Helical and Point-to-Axial Chirality Transmission and Induction of Optical Activity in Multichromophoric Systems: Basic Principles and Relevant Applications in Chirality Sensing

Symmetry, Journal Year: 2025, Volume and Issue: 17(2), P. 293 - 293

Published: Feb. 14, 2025

The analysis of natural and artificial chiral compounds is vital wherever the nuances in three-dimensional structure are decisive for possibility their further use, e.g., as pharmaceuticals or catalysts. qualitative determination a entity requires either an anomalous scattering X-ray radiation chiroptical techniques, which electronic circular dichroism (ECD) one most useful. Chiroptical sensing that uses stereodynamic probes remains remedies problem lack suitable chromophore molecules compound. A covalent non-covalent binding ECD-silent molecule (the inducer) to UV-active chromophoric system (chiroptical probe) led obtaining complex ECD active at given spectral region. transfer structural information from permanently inducer structurally labile probe results adjusting latter’s environment. This contribution focuses on some fundamental aspects chirality using conformationally probes. It discusses mechanism action arbitrarily chosen sensors, with particular emphasis based di- triarylmethyl derivatives biphenyl its congeners.

Language: Английский

---

Theoretical Investigations on [3,3] Sigma tropic Rearrangements in 1‐Formyl‐2‐Vinyl Cyclobutane/Lactam

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(12)

Published: March 1, 2025

Abstract The current manuscript discusses the density functional based ab initio investigations of [3,3] oxa‐Claisen rearrangement reactions involving functionalized 1‐formyl‐2‐vinyl cyclobutane/lactam, emphasizing their expected transformations into various 8 membered heterocycles. most feasible molecular assembly for targeted cyclobutane/lactam has been identified. Reaction parameters, including reaction and activation energies, have calculated compared. theoretical effect substituents (H, Ph, SO 2 Ph) at different positions tethered 4‐vinyl 3‐oxa functionalities cyclobutane/lactams also studied proposed carba‐Claisen cyclobutane/lactam. Our findings suggest an energy barrier ranging from 50 to 100 kcal/mol rearrangements. We observed a reduction in 20 52 with polar solvent, whereas decrease 30 was noted nonpolar solvent. Claisen 2‐vinyl carba‐aldehydes demonstrates exothermic reaction.

Language: Английский

---

The application and development of cyanating reagents in asymmetric cyanation reactions

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155549 - 155549

Published: March 1, 2025

Language: Английский

---

Transition Metal‐Catalyzed Direct Functionalization of Carbazoles

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

Published: April 29, 2025

Abstract Carbazoles are an important class of nitrogen‐containing heterocycles found in diverse natural products, bioactive molecules, and functional materials. Their broader applications have driven extensive research into their synthesis functionalization. Among various approaches, transition metal‐catalyzed C−H activation has emerged as a powerful tool for direct functionalization, offering regioselectivity, efficiency, sustainability. This review comprehensively summarizes advancements functionalization carbazoles. Various catalytic systems employing palladium, ruthenium, rhodium, nickel, cobalt, copper, iron enabled alkylation, alkenylation, acylation, arylation, alkynylation, heteroatom incorporation These methodologies late‐stage diversification opened avenues accessing structurally complex carbazole derivatives with tailored properties. The aims to provide comprehensive guide researchers exploring via activation, highlighting key mechanistic insights, scope, emerging trends this field.

Language: Английский

---

Recent advances in chirality sensing/recognition using supramolecular macrocycles

Supramolecular Materials, Journal Year: 2025, Volume and Issue: 4, P. 100107 - 100107

Published: May 14, 2025

Language: Английский

---

Synthesis and resolution of a 1,1′-biazulene analogue of BINOL

RSC Advances, Journal Year: 2025, Volume and Issue: 15(19), P. 14881 - 14892

Published: Jan. 1, 2025

Biaryls exhibiting axial chirality have been extensively exploited in fields such as asymmetric catalysis, but the biaryl linkage typically consists of benzenoid aromatic rings, with non-benzenoid biaryls being scarce. Here we report first preparation a (non-benzenoid) 1,1'-biazulene-2,2'-diol ("1,1'-BAzOL") enantiopure form and determine its barrier to racemisation. Furthermore transformed into corresponding 2,2'-bis(phosphonate), thereby demonstrating functional group interconversion through cross coupling highlighting potential for diversification.

Language: Английский

---

Asymmetric heterogeneous catalysis using crystalline porous materials

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review discusses the design and synthesis methods asymmetric catalytic applications of chiral crystalline porous materials, focusing on heterogeneous reactions control mechanisms.

Language: Английский

---

Stimuli-Responsive Photoluminescent Molecular Tweezers for Highly Enantioselective Discrimination of Chiral Primary Amines

Analytical Chemistry, Journal Year: 2024, Volume and Issue: 96(49), P. 19632 - 19640

Published: Nov. 27, 2024

To address the challenge of chiral recognition in terms efficiency and generality, we propose a novel fluorescence sensing approach by rationally designing metal-ion-responsive molecular tweezers. The flexible adaptable tweezers enable facile 31 structurally varied primary amine compounds, including amino acids, acid esters, amines. Notably, upon stimulation zinc ions, demonstrate higher enantioselective response. Combined density functional theory calculations reveal that mechanism relies on differential reaction rates potential hydrogen-bonding interactions between two enantiomers receptor, which results one forming more abundant, stable, rigid complex with resulting significant increase intensity enantioselectivity. stimuli-responsive provides strategy for precise stereocontrol universality recognition, offering promising tool applications various fields.

Language: Английский

---

Absolute Helix‐Sense‐Selective Polymerization Using Circularly Polarized Light in One‐Handed Helical Channels

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Abstract Absolute helix‐sense‐selective polymerization of an achiral acetylene monomer ( 1 ) in one‐handed helical channels created with decomposition (±)‐poly using circularly polarized light is realized no chiral compounds. In addition, the relative optical yield (%ee) formed oligomers controlled by those channels.

Language: Английский

---