A Regioselective [3 + 2] Cycloaddition of Alkynols and Ketones To Access Diverse 1,3-Dioxolane Scaffolds DOI
Ganesh Kumar Dhandabani,

Jeyakannu Palaniraja,

Chia-Ling Shih

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(1), P. 719 - 724

Published: Dec. 27, 2023

This study presents a stepwise exoselective [3 + 2] cycloaddition reaction of alkynols with ketones, leading to the synthesis 4-methylene-1,3-dioxolane derivatives. Remarkably, without any Thorpe–Ingold induced effect, cyclization was demonstrated complete regio- and chemoselectivity, which solely promoted by cesium carbonate. A wide range unactivated ketones are viable under these mild conditions, both primary tertiary compatible reactions. We have prepared diverse array highly dense exomethylene 1,3-dioxolane rings demonstrating remarkable tolerance for various functional groups.

Language: Английский

Regioselective Aryne Annulations of N-Tosyl-2-enamides and N-tert-Butylsulfinyl-2-enamides for the Construction of Dihydroquinolin-4-one and Chroman-4-imine Units DOI
Aimin Zhang,

Suh Young Yu,

Jihye Lee

et al.

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

Published: Feb. 14, 2025

A regioselective synthesis of the dihydroquinolin-4-one 4 is achieved from aryne-mediated annulation an o-(trimethylsilyl)aryl triflate 1 with N-tosyl-2-enamide 2 in presence TBAT toluene, whereas chroman-4-imine 5 formed reaction N-(tert-butylsulfinyl)-2-enamide 3 and TBAF THF. Governing factors for regioselectivity have been accounted as strong steric electronic effects between N-toluenesulfonyl N-tert-butylsulfinyl groups 3. The methods described herein are successful various substrates or high levels regioselectivity, diastereoselectivity 5.

Language: Английский

Citations

0
Visible light-driven dearomative meta-cycloadditions of 2-acetonaphthalenes via triplet energy transfer cascade DOI Creative Commons

Pramod Rai,

Sanghamitra Naik,

Kriti Gupta

et al.

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

Published: March 27, 2025

Dearomative cycloadditions (DACs) with ortho- and para-variants have been well documented under visible light-mediated triplet-triplet energy transfer (VLEnT) catalysis. The prospective [3 + 2] or the meta-DACs propelled via VLEnT catalysis remains elusive. Classically, are known harsher UV irradiations symmetry allowed in excited singlet potential surface. Herein, we report formal of 2-acetonaphthalenes propagated a two-step cascade circumventing attainment energetically higher states. photosensitizer selectively promotes [4 cycloaddition followed by contra-thermodynamic di-π-methane type skeleton rearrangement cascade. DFT studies conjugation electrochemical, photoluminescence, kinetic, quadratic dependency, control experiments support described protocol delivers highly sp3-rich polycyclic frameworks high yields wide functional group tolerance. inclusion bioactive molecules establishment array post-synthetic derivatizations further underscores adaptability methodology for generating complex three-dimensional molecules. reactions acknowledged their capacity to rapidly efficiently generate molecular complexity, creating sp3-enriched 3D from simple 2D aromatic feedstocks. Here, authors dearomative meta-cycloaddition

Language: Английский

Citations

0
Catalytic Atroposelective Synthesis of Axially Chiral Azomethine Imines and Neuroprotective Activity Evaluation DOI
Qian‐Qian Yang, Chen Chen,

Dahong Yao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Nov. 30, 2023

Azomethine imines, as a prominent class of 1,3-dipolar species, hold great significance and potential in organic medicinal chemistry. However, the reported synthesis centrally chiral azomethine imines relies on kinetic resolution, construction axially remains unexplored. Herein, we present through copper- or phosphoric acid catalyzed ring-closure reactions N'-(2-alkynylbenzylidene)hydrazides, showcasing high efficiency, mild conditions, broad substrate scope, excellent enantioselectivity. Furthermore, biological evaluation revealed that synthesized effectively protect dorsal root ganglia (DRG) neurons by inhibiting apoptosis induced oxaliplatin, offering promising therapeutic approach for chemotherapy-induced peripheral neuropathy (CIPN). Remarkably, (S)- (R)-atropisomers displayed distinct neuroprotective activities, underscoring axial stereochemistry.

Language: Английский

Citations

6
Bioactive atropisomers: Unraveling design strategies and synthetic routes for drug discovery DOI
Shuai‐Jiang Liu, Qian Zhao, Xiaochen Liu

et al.

Medicinal Research Reviews, Journal Year: 2024, Volume and Issue: 44(5), P. 1971 - 2014

Published: March 21, 2024

Atropisomerism, an expression of axial chirality caused by limited bond rotation, is a prominent aspect within the field medicinal chemistry. It has been shown that atropisomers wide range compounds, including established FDA-approved drugs and experimental molecules, display markedly different biological activities. The time-dependent reversal in poses complexity obstacles process drug discovery development. Nonetheless, recent progress understanding atropisomerism enhanced characterization methods have greatly assisted chemists effective development atropisomeric molecules. This article provides comprehensive review their special design thoughts, synthetic routes, activities, serving as reference for synthesis evaluation bioactive future.

Language: Английский

Citations

1
Utilizing Visible Light to Enable Contra-Thermodynamic Skeletal Rearrangement for Dearomative meta-Cycloadditions of 2-Acetonaphthalenes via Triplet Energy Transfer Cascade DOI Creative Commons

Pramod Rai,

Sanghamitra Naik,

Kriti Gupta

et al.

Published: March 25, 2024

With the renaissance of visible light-mediated triplet-triplet energy transfer (VLEnT) catalysis as a greener and milder catalytic regime, dearomative cycloadditions (DAC) have emerged powerful arsenal in arriving at sophisticated three-dimensional molecular scaffolds. ortho- para-variants having been well documented under VLEnT meta-cycloadditions being known to be symmetry allowed excited singlet potential surface harsher UV irradiations, prospective [3 + 2] propelled via remains elusive. Herein, we report formal meta-cycloaddition 2-acetonaphthalenes propagated two-step cascade circumventing attainment energetically higher states. The work showcases judicious selection photosensitizer backed by DFT calculations selectively promote [4 DAC followed contra-thermodynamic stepwise skeleton rearrangement cascade. detailed studies conjugation with electrochemical, photoluminescence, kinetic, quadratic dependency, control experiments support observed meta-selectivity over para-DAC was rationalized reactivity difference triplet spin surfaces. described protocol delivers highly sp3-rich polycyclic frameworks high yields moderate selectivities wide functional group tolerance. inclusion bioactive agents establishment array post-synthetic derivatizations further climaxes efficiency designed protocol.

Language: Английский

Citations

1
Controlling Diastereoselectivity in Dearomatizing Diels‐Alder Reactions of Nitroarenes with 2‐Trimethylsilyloxycyclohexadiene DOI Creative Commons
Marian Powderly, Mélanie Roseau, Gilles Frison

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(34)

Published: April 15, 2024

Dearomative Diels-Alder cycloadditions between nitroarenes and 2-trimethylsilyloxycyclohexadiene are carried out under high pressure at room temperature in the absence of any chemical promoter. Reactions performed with different arenes, including highly aromatic naphthalenes quinolines. They lead to 3D-scaffolds exquisite exo-diastereoselectivity. The exo approach is characterized by lower distortion substrates a late TS more favorable orbital interactions presumably nitro group dienic part, explaining stereoselectivity.

Language: Английский

Citations

1
A kinetic resolution accompanied chirality transformation process for asymmetric synthesis of chiral phenol, oxaziridine, and α-hydroxyl cyclic ketone DOI
Pengxin Wang, Xiaoyong Zhang, Lingqing Wang

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(9), P. 2989 - 2997

Published: Aug. 8, 2024

Language: Английский

Citations

1
Substituent‐Controlled Regiodivergent Palladium‐Catalyzed Annulative Dearomatization of Phenols toward Skeletally Diverse Spirocyclohexadienones DOI

Hui‐Lin Mao,

Jun Yu,

Yi‐Ting Shen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(18), P. 3075 - 3081

Published: July 28, 2023

Abstract A palladium‐catalyzed intermolecular dearomative formal [4+2] annulation of phenols with propargyl electrophiles is reported, enabling substituent‐controlled regiodivergent synthesis a wide range skeletally diverse spirocyclohexadienones good yields. The regiodivergence could be precisely controlled by adjusting the steric hindrance O ‐ and N ‐substituents from binucleophilic substrates, where substrates an ‐nucleophilic site were converted into spiro[chromane‐4,1′‐cyclohexane]‐2′,5′‐dien‐4′‐ones complete regioselectivity ( Z )‐selectivity, whereas ‐nucleophiles enabled different process to access spiro[cyclohexane‐1,4′‐quinoline]‐2,5‐dien‐4‐ones.

Language: Английский

Citations

2
Organophosphoric Acid Catalyzed [3＋3] Cyclization for the Synthesis of Indenoquinolinedione Derivatives DOI

Xinyan Guo,

Hong Yu,

Hong‐Lin Wan

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(12), P. 3727 - 3727

Published: Jan. 1, 2024

Language: Английский

Citations

0
Catalytic Atroposelective Synthesis of Axially Chiral Azomethine Imines and Neuroprotective Activity Evaluation DOI
Qian‐Qian Yang, Chen Chen,

Dahong Yao

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(5)

Published: Nov. 30, 2023

Abstract Azomethine imines, as a prominent class of 1,3‐dipolar species, hold great significance and potential in organic medicinal chemistry. However, the reported synthesis centrally chiral azomethine imines relies on kinetic resolution, construction axially remains unexplored. Herein, we present through copper‐ or phosphoric acid catalyzed ring‐closure reactions N ′‐(2‐alkynylbenzylidene)hydrazides, showcasing high efficiency, mild conditions, broad substrate scope, excellent enantioselectivity. Furthermore, biological evaluation revealed that synthesized effectively protect dorsal root ganglia (DRG) neurons by inhibiting apoptosis induced oxaliplatin, offering promising therapeutic approach for chemotherapy‐induced peripheral neuropathy (CIPN). Remarkably, ( S )‐ R )‐atropisomers displayed distinct neuroprotective activities, underscoring axial stereochemistry.

Language: Английский

Citations

0