Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides DOI
Shi Cao, Doyoung Kim, Wooseok Lee

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(46)

Published: Oct. 2, 2023

Abstract This research explores the enantioselective hydrosulfonylation of various α,β‐unsaturated carbonyl compounds via use visible light and redox‐active chiral Ni‐catalysis, facilitating synthesis enantioenriched α‐chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing reactivity between metal‐coordinated moderate electrophilic sulfonyl radicals, aiming to minimize background reactions. The success our approach stems from two distinctive attributes: 1) Cl‐atom abstraction employed for radical generation chlorides, 2) single‐electron reduction produce a key enolate Ni‐complex. latter process appears enhance feasibility radical's addition electron‐rich radical. An in‐depth investigation into reaction mechanism, supported by both experimental observations theoretical analysis, offers insight intricate process. Moreover, versatility methodology is highlighted through its successful application in late‐stage functionalization complex bioactive molecules, demonstrating practicality as strategy producing sulfones.

Language: Английский

Photocatalytic Sulfonylation: Innovations and Applications DOI
Anxiang Huang,

Rui Li,

Qi‐Yan Lv

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 14, 2024

Photosynthesis, converting sustainable solar energy into chemical energy, has emerged as a promising craft to achieve diverse organic transformations due its mild reaction conditions, sustainability, and high efficiency. The synthesis of sulfonated compounds drawn significant attention in the pharmaceuticals, agrochemicals, materials industries unique structure electronic properties sulfonyl groups. Over past decades, many photocatalytic sulfonylation reactions have been developed. In this review, recent advances photocatalyzed reviewed since 2020, with primary focus on discussing design mechanism.

Language: Английский

Citations

9
Photocatalytic Enantioselective Hydrosulfonylation of α,β‐Unsaturated Carbonyls with Sulfonyl Chlorides DOI
Shi Cao, Doyoung Kim, Wooseok Lee

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Oct. 2, 2023

This research explores the enantioselective hydrosulfonylation of various α,β-unsaturated carbonyl compounds via use visible light and redox-active chiral Ni-catalysis, facilitating synthesis enantioenriched α-chiral sulfones with remarkable enantioselectivity (exceeding 99 % ee). A significant challenge entails enhancing reactivity between metal-coordinated moderate electrophilic sulfonyl radicals, aiming to minimize background reactions. The success our approach stems from two distinctive attributes: 1) Cl-atom abstraction employed for radical generation chlorides, 2) single-electron reduction produce a key enolate Ni-complex. latter process appears enhance feasibility radical's addition electron-rich radical. An in-depth investigation into reaction mechanism, supported by both experimental observations theoretical analysis, offers insight intricate process. Moreover, versatility methodology is highlighted through its successful application in late-stage functionalization complex bioactive molecules, demonstrating practicality as strategy producing sulfones.

Language: Английский

Citations

20
An Expedient Radical Approach for the Decarboxylative Synthesis of Stereodefined All‐Carbon Tetrasubstituted Olefins DOI
Qian Zeng,

Yamini Nirwan,

J. Benet‐Buchholz

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 15, 2024

We report a user-friendly approach for the decarboxylative formation of stereodefined and complex tri- tetra-substituted olefins from vinyl cyclic carbonates amines as radical precursors. The protocol relies on easy photo-initiated α-amino-radical followed by addition onto double bond substrate resulting in sequence involving carbonate ring-opening, relay, CO

Language: Английский

Citations

4
Enantioselective Pd- and Cu-Catalyzed Hydrofunctionalization of Methylenecyclopropanes via a Distal C–C Bond Cleavage DOI
Jie Zhao,

Deyue Ren,

Jintao Xia

et al.

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

Published: Jan. 28, 2025

The enantioselective ring-opening reactions of methylenecyclopropanes (MCPs) involving C–C bond activation via oxidative addition transition metals have been rarely reported. Here, we disclose a Pd/Cu-catalyzed enantio- and regioselective coupling between cyclic imino esters MCPs to produce α-allylated 2H-pyrrole derivatives. In this reaction, azomethine ylide formed by chiral copper catalyst with ketimine ester would serve as nucleophile react activated palladium catalysis. This bimetallic system exhibited broad substrate scope high regio- enantioselectivities.

Language: Английский

Citations

0
Highly Functional Allyl-Bicyclo[1.1.1]pentane Synthesis by Radical-Initiated Three-Component Stereoselective Allylation DOI Creative Commons
Qian Zeng,

Wangyu Shi,

Arjan W. Kleij

et al.

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 913 - 921

Published: Feb. 11, 2025

Rapid access to highly functional allylated BCP synthons can be achieved with good selectivity and yield through a radical, three-component reaction (3CR) regime using various combinations of radical precursors vinyl-appended heterocycles acting as versatile modular precursors. This practical process combines mild operating conditions, wide scope partners, the ability diversify functionalized allylic scaffolds further allyl other groups synthetic branching points. The developed protocol allows structural alteration increases molecular complexity late-stage drug modifications conjugation approaches. Mechanistic probes demonstrate that 3CR is initiated by selective, light-promoted addition [1.1.1]-propellane, followed coupling vinyl-substituted heterocycle, which represents formal decarboxylative addition/double bond relay/protonation sequence.

Language: Английский

Citations

0
Green Synthesis of 1,4-Dihydropyridines through Catalyst-Free Multicomponent Hantzsch Reaction in an Undergraduate Teaching Laboratory DOI
Yan Zhang,

Xiuya Ma,

Xinyu Zhou

et al.

Journal of Chemical Education, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Multicomponent reactions (MCRs) are fascinating chemical processes where three or more starting materials come together to form a single product. By exploring various MCRs, second-year undergraduate students learn about the synergy between different functional groups and how they influence reactivity, power of streamlined approach compared conventional stepwise reactions, critical thinking MCR mechanisms. Herein, we introduce valuable synthetic method for constructing heterocyclic compounds through multiple-component condensation/cycloaddition process. Specifically, focus on 1,4-dihydropyridine (1,4-DHP), privileged N-heterocyclic scaffold widely used in medicinal chemistry, particularly 4-aryl-3,5-dicarboxylated derivatives. The experiment provides an excellent opportunity explore concept green chemistry while synthesizing structurally interesting useful molecules using readily available materials. achieve this condensation reaction 2-furaldehyde (furfural), acetoacetic acid tert-butyl ester, ammonium acetate. Key features teaching include following. (1) reaction: involves concise, multicomponent with short time. (2) Catalyst-free: Notably, proceeds without need solvents catalysts. (3) Visually striking system: change system is visually evident, enhancing learning experience. (4) Useful methodology drug synthesis: has practical implications synthesis. We successfully implemented proposal across five parallel student groups, involving approximately 150 participants. experimental procedures encompass organic synthesis, thin-layer chromatography (TLC), nuclear magnetic resonance (NMR) analysis.

Language: Английский

Citations

0
Photocatalytic Site‐Selective Cascade Radical Addition of Biaryl Ynones for the Construction of Spiro‐ and Fused Carbon Rings DOI
Kairui Liu,

Chunhang Zhao,

Liji Gu

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(14), P. 1599 - 1605

Published: March 13, 2024

Comprehensive Summary Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules. Ynones are good regional selectivity acceptors in organic synthesis, and many of bio‐relevant cyclic compounds could be easily obtained by direct cyclization reaction. Here, we report a photocatalytic cascade addition biaryl ynones, the divergent synthesis privileged carbon cycles. Additionally, further transformation multi‐functional group product into variety other derivatives demonstrates synthetic value this developed method.

Language: Английский

Citations

3
Radical Ring-Opening Fluorosulfonylation of Methylenecyclobutanols via Electron Donor–Acceptor Photoactivation DOI
Tianyu He,

Chaoqiang Liang,

Ping Jiang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(26), P. 5577 - 5581

Published: June 24, 2024

A visible-light-mediated catalyst- and additive-free method for radical ring-opening fluorosulfonylation of methylenecyclobutanols is reported. Sulfuryl chlorofluoride acts as a FSO

Language: Английский

Citations

3
Photocatalytic Synthesis and Functionalization of Sulfones, Sulfonamides and Sulfoximines DOI
José J. Garrido‐González, Katy Medrano‐Uribe, Cristian Rosso

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(44)

Published: July 22, 2024

Sulfur(VI)-based functional groups are popular scaffolds in a wide variety of research fields including synthetic and medicinal chemistry, as well chemical biology. The growing interest sulfur(VI)-containing molecules has motivated the scientific community to explore new methods synthesize modify them. Here, photocatalysis plays key role granting access types reactivity under mild reaction conditions. In this Perspective, we present selection works reported last six years focused on photocatalytic assembly sulfones, sulfonamides, sulfoximines. We addressed intermediates for each transformation, while discussing limitations strength points protocols. Future directions field finally presented.

Language: Английский

Citations

3
Site-Selective C8-Alkylation of Quinolines with Cyclopropanols: Merging C–H/C–C Bond Activation DOI
Santu Mandal, Tripti Paul, Pallab Karjee

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(43), P. 7805 - 7809

Published: Oct. 23, 2023

The site-selective C8-alkylation of quinolines has been accomplished using cyclopropyl alcohols as the alkylating agents and N-oxide a weak chelating group in presence Co(III) catalysis via merging C-H/C-C bond activation. use cyclopropanol alkyl source, Co catalysis, substrate scope, HRMS analysis reaction intermediate, late-stage mutation drug molecules/natural products are important practical features.

Language: Английский

Citations

7