Kinetic Resolution of Azaarylethynyl Tertiary Alcohols by Chiral Brønsted Acid Catalysed Phosphine‐Mediated Deoxygenation DOI
Guanghui Wang, Lulu Li,

Yifeng Jiang

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 135(4)

Published: Nov. 22, 2022

Abstract A chiral Brønsted acid catalysed phosphine‐mediated deoxygenation protocol is reported. This metal‐free method provides a precise kinetic resolution platform for azaarylethynyl tertiary alcohols, which are broad category of biologically and synthetically important azaarene derivatives. In addition to providing an efficient the first asymmetric preparation these strategy facilitates construction azaaryl‐functionalized allenes with good excellent enantioselectivities. The high selectivity factors ( s up 235), substrate scope, ability convert azaaryl compounds into both alcohols robustly underscore efficiency promising utility this method. practicability further validated by successful synthesis deuterated ee values substantial incorporation deuterium using inexpensive D 2 O as source.

Language: Английский

Intermolecular 1,2-Difunctionalization of Terminal Alkynes to Access Trisubstituted Alkenes via Copper/Photoredox Dual Catalysis DOI
Fei Tang, Yi‐Si Feng, Zhi-Fei Cheng

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(21), P. 3916 - 3921

Published: May 22, 2023

We report a copper metallaphotocatalytic 1,2-difunctionalization of terminal alkynes with N-hydroxyphthalimide (NHP) esters and readily available silyl reagents (TMSCN TMSNCS) to access stereodefined trisubstituted alkenes, including (E)-alkenyl nitriles thiocyanates. The reaction proceeds excellent anti-stereoselectivity demonstrates broad compatibility wide range NHP as alkyl radical precursors. Experimental computational studies have been performed gain insight into the mechanism.

Language: Английский

Citations

9
Visible‐Light‐Mediated [2+2] Photocycloadditions of Alkynes DOI
Qing‐Bao Zhang,

Feng Li,

Bin Pan

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 29, 2024

Visible-light-mediated [2+2] photocycloaddition reaction can be considered an ideal solution due to its green and sustainable properties, is one of the most efficient methods synthesize four-membered ring motifs. Although research on alkynes challenging because diminished reactivity alkynes, more significant strain products, remarkable achievements have been made in this field. In article, we highlight recent advances visible-light-mediated reactions with focus mechanism late-stage synthetic applications. Advances obtaining cyclobutenes, azetines, oxetene active intermediates continue breakthroughs fascinating field research.

Language: Английский

Citations

3
Metallaphotoredox Synthesis of Axially Chiral Tetrasubstituted Allenes through Regio- and Enantioselective 1,4-Carbocyanation of 1,3-Enynes DOI

Keyi Peng,

Ya-Sheng Cao,

Quanyuan Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(18), P. 14048 - 14057

Published: Sept. 10, 2024

Language: Английский

Citations

3
Visible Light-Promoted Three-Component Reaction for the Synthesis of Pyrrolopyrazoles DOI

Han‐Peng Pan,

Shao‐Shuai Chen,

Han Yang

et al.

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

Published: April 15, 2025

A visible light-enabled three-component cascade assembles pyrrolopyrazoles from arylalkynes, benzoquinones, and 5-aminopyrazole through a mechanistically validated carbonyl-alkyne metathesis/(3 + 2)-cycloaddition/1,2-aryl migration sequence. This protocol delivers pyrrolopyrazole heterocycles in up to 96% yield with excellent functional group tolerance. Preliminary biological screening identified promising antitumor activity selected products, highlighting the potential value of this method. The proposed reaction mechanism is supported by control experiments.

Language: Английский

Citations

0
Remote Stereocontrol in the C6-Functionalization of Indoles via Synergistic Ion-Pair Catalysis DOI
Zhi‐Qiang Zhu,

Han‐Peng Pan,

Long Liang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 9897 - 9908

Published: May 28, 2025

Language: Английский

Citations

0
Enantioselective synthesis of α,α-diarylketones by sequential visible light photoactivation and phosphoric acid catalysis DOI Creative Commons
Hong‐Fu Liu, Long Liang, Zhiqiang Zhu

et al.

Science Advances, Journal Year: 2023, Volume and Issue: 9(24)

Published: June 16, 2023

Chiral ketones and their derivatives are useful synthetic intermediates for the synthesis of biologically active natural products medicinally relevant molecules. Nevertheless, general broadly applicable methods enantioenriched acyclic α,α-disubstituted ketones, especially α,α-diarylketones, remain largely underdeveloped, owing to easy racemization. Here, we report a visible light photoactivation phosphoric acid–catalyzed alkyne-carbonyl metathesis/transfer hydrogenation one-pot reaction using arylalkyne, benzoquinone, Hantzsch ester expeditious α,α-diarylketones with excellent yields enantioselectivities. In reaction, three chemical bonds, including C═O, C─C, C─H, formed, providing de novo chiral α,α-diarylketones. Moreover, this protocol provides convenient practical method synthesize or modify complex bioactive molecules, efficient routes florylpicoxamid BRL-15572 analogs. Computational mechanistic studies revealed that C-H/π interactions, π-π interaction, substituents all play crucial roles in stereocontrol reaction.

Language: Английский

Citations

7
Electroenzymatic cascade reaction on a biohybrid boosts the chiral epoxidation reaction DOI
Xuefang Zhu, Yu Ding, Shu-Ni Li

et al.

Science Bulletin, Journal Year: 2023, Volume and Issue: 69(4), P. 483 - 491

Published: Dec. 12, 2023

Language: Английский

Citations

7
Visible light induced reactions of quinones DOI

Jeffrey Jang,

G.‐H. LEE,

Eun Jin Cho

et al.

Bulletin of the Korean Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 17, 2024

Abstract This review covers the visible light induced reactions of quinones such as benzoquinone, naphthoquinone, and anthraquinone. These are distinguished by their fully conjugated structures, which feature minimal energy gaps, nonbonding electron pairs on oxygen atoms. Such structural attributes facilitate n p → π* transition, allowing for easy access to excited states rendering highly reactive under visible‐light irradiation. We describe three primary types facilitated these electronic characteristics: Paternò–Büchi (PB) reactions, entail [2 + 2] photocycloaddition between carbonyl groups alkenes or alkynes; CH activation processes, showcase quinones' versatility in functionalizing hydrocarbons; formation donor–acceptor complexes, demonstrating capability engage charge transfer interactions. Through this review, we highlight critical role play photochemistry, unique properties, broad applicability synthetic organic chemistry.

Language: Английский

Citations

2
Substrate-Controlled Diastereo- and Enantiodivergent Synthesis of Bis-Spirocyclopropyloxindoles from Available Isatin as a Single Starting Material DOI
Mehdi Eskandari, Khosrow Jadidi, Behrouz Notash

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5254 - 5274

Published: April 21, 2023

The first diastereo- and enantiodivergent asymmetric synthesis of new bis-spirocyclopropyloxindole scaffolds has been accomplished from the readily available isatin as a single starting material. Four rel-(1R,2R,3R), rel-(1S,2S,3R), rel-(1R,2R,3S), rel-(1S,2S,3S) configurations desired products were constructed in excellent enantiopurity via simple switch substrates using chiral auxiliary-controlled method. absolute configuration cycloadducts with three contiguous quaternary/tertiary stereogenic centers was confirmed through X-ray diffraction analysis. A facile versatile precursor 3-chlorooxindoles also introduced.

Language: Английский

Citations

4
Carbofunctionalization of Terminal Alkynes via Rhodium Catalysis Enabling Formations of Four Different Bonds DOI

Dae‐Kwon Kim,

Minjung Keum,

Hee-Kyung Yun

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2024 - 2029

Published: March 17, 2023

Described here is the oxygenative carbofunctionalization of terminal alkynes mediated by combined rhodium catalysis that enables regioselective quadruple formation C–C, C–H, C–O, and C–heteroatom bonds. Mechanistic studies suggest a disubstituted vinylidene complex generated upon C–C bond at alkyne with tethered electrophiles such as alkyl halides, aldehydes, imines, Michael acceptors. Subsequent intermolecular transfer oxygenation pyridine N-oxide generates rhodium-complexed ketene intermediate reacts variety heteroatom nucleophiles to give rise cyclic carboxylic acid derivatives.

Language: Английский

Citations

3