Carbene-Catalyzed Enantioselective Addition of Sulfinate to Ketones DOI
Rui Deng,

Mingyi Pan,

Jianjian Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4394 - 4399

Published: May 14, 2024

A carbene-catalyzed enantioselective addition of sulfinate to ketones between 2-benzoylbenzaldehyde and sulfonyl chloride is disclosed. Up now, the carbon heteroatom nucleophiles have effectively undergone catalytic carbonyl molecules introduce functionalities chirality. Sulfone, as an important class sulfur-containing functional groups, represents highly valuable motifs in medicines natural products. It remains undeveloped for asymmetric carbonyls. Herein we disclosed first synthesis sulfones via N-heterocyclic carbene (NHC) catalysis. The behaves both oxidant a nucleophilic substrate this process. Experimental studies suggested that Breslow intermediate can be SET oxidized by generate radical. This novel synthetic approach carbonyls also used modify commercially available molecules.

Language: Английский

Electrochemically promoted N-heterocyclic carbene polymer-catalyzed cycloaddition of aldehyde with isocyanide acetate DOI

Chuhong Ou,

Ying‐Ming Pan, Haitao Tang

et al.

Science China Chemistry, Journal Year: 2022, Volume and Issue: 65(10), P. 1873 - 1878

Published: Sept. 15, 2022

Language: Английский

Citations

55
N-Heterocyclic Carbene-Catalyzed Remote Enantioselective C–C Bond Formation via 1,6-Addition with Formyl Enynes DOI

Xiaolin Peng,

Yixian Huang,

Wei Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 2127 - 2133

Published: Jan. 25, 2024

N-Heterocyclic carbenes (NHCs) have emerged as powerful organocatalysts in controlling the stereoselectivities of reaction sites that are remote from catalyst-binding position. Meanwhile, construction a stereogenic center at δ-position through NHC catalysis remains an unmet goal. Herein, we report NHC-catalyzed enantioselective 1,6-conjugated addition formyl enynes with nucleophiles oxidative LUMO activation strategy. The enables efficient chirality control enyne substrates, providing access to high-value-added enantio-enriched pyrano[2,3-b]indole and pyrano[2,3-c]pyrazole derivatives. In addition, central-to-axial transfer oxidation our products was realized, enabling facile axially chiral pyrans.

Language: Английский

Citations

11
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
Multicomponent Sulfonylation of Alkenes to Access β-Substituted Arylsulfones DOI

Kai‐Yi Zhang,

Fang Long,

Chuan‐Chong Peng

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3772 - 3780

Published: March 6, 2023

A novel multicomponent sulfonylation of alkenes is described for the assembly various β-substituted arylsulfones using cheap and easily available K2S2O5 as a sulfur dioxide source. Of note, procedure does not need any extra oxidants metal catalysts exhibits relatively wide substrate scope good functional group compatibility. Mechanistically, an initial arylsulfonyl radical formed involving insertion with aryl diazonium salt, followed by alkoxyarylsulfonylation or hydroxysulfonylation alkenes.

Language: Английский

Citations

17
Enantioselective Synthesis of Allylic Sulfones via Rhodium-Catalyzed Direct Hydrosulfonylation of Allenes and Alkynes DOI
Chieh‐Yu Chang, Aaron Aponick

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(25), P. 16996 - 17002

Published: June 14, 2024

A highly regio- and enantioselective hydrosulfonylation using commercially available sodium sulfinates is reported, providing the first direct asymmetric rhodium-catalyzed of allenes/alkynes to synthesize chiral allylic sulfones. Ligand screening studies demonstrated indispensable role C1-symmetric P,N-ligand (Rax,S,S)-StackPhim for achieving both high regioselecitivity (>20:1) enantioselectivity (up 97% ee). Notably, operationally simple method mild conditions allow rapid preparation sulfones with a wide scope functional groups. Moreover, use tert-butyldimethylsilyloxymethanesulfinate enables collective synthesis various sulfone derivatives after transformations protected hydroxymethyl product.

Language: Английский

Citations

8
Recent advances in catalytic asymmetric synthesis DOI Creative Commons

Ashna Garg,

Dominick Rendina,

Hersh Bendale

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: May 9, 2024

Asymmetric catalysis stands at the forefront of modern chemistry, serving as a cornerstone for efficient creation enantiopure chiral molecules characterized by their high selectivity. In this review, we delve into realm asymmetric catalytic reactions, which spans various methodologies, each contributing to broader landscape enantioselective synthesis molecules. Transition metals play central role catalysts wide range transformations with ligands such phosphines, N -heterocyclic carbenes (NHCs), etc., facilitating formation C-C and C-X bonds, enabling precise control over stereochemistry. Enantioselective photocatalytic reactions leverage power light driving force electrocatalysis has emerged sustainable approach, being both atom-efficient environmentally friendly, while offering versatile toolkit reductions oxidations. Biocatalysis relies on nature’s most catalysts, i.e., enzymes, provide exquisite selectivity, well tolerance diverse functional groups under mild conditions. Thus, enzymatic optical resolution, kinetic resolution dynamic have revolutionized production compounds. organocatalysis uses metal-free organocatalysts, consisting modular phosphorus, sulfur nitrogen components, remarkably transformations. Additionally, unlocking traditionally unreactive C-H bonds through selective functionalization expanded arsenal synthesis, atom-economical construction Incorporating flow chemistry been transformative, continuous systems reaction conditions, enhancing efficiency optimization. Researchers are increasingly adopting hybrid approaches that combine multiple strategies synergistically tackle complex synthetic challenges. This convergence holds great promise, propelling field forward in form. As these methodologies evolve complement one another, they push boundaries what can be accomplished leading discovery novel, highly may lead groundbreaking applications across industries.

Language: Английский

Citations

7
Exploring Molecular Complexity by N‐Heterocyclic Carbene Organocatalysis: New Activation and Reaction Diversity DOI

Yonggui Liu,

Yanyan Wang, Xingxing Wu

et al.

The Chemical Record, Journal Year: 2022, Volume and Issue: 23(7)

Published: Nov. 7, 2022

Abstract The development of catalytic synthetic approaches towards molecular complexity from simple materials continues to be an ultimate goal in chemistry. Over the past decades, N‐heterocyclic carbene (NHC) organocatalysis has been extensively investigated provide opportunities for a vast number novel chemical transformations. Various activation modes and reactive intermediates enabled by NHC small‐molecule catalysts, such as Breslow intermediates, (homo)enolates, acyl azoliums their derived unsaturated exhibit great potential construction complicated skeletons. This personal account will summarize our group's recent work exploration new catalysis with focus on applications achieve diversity enantioselectivity preparation functional molecules.

Language: Английский

Citations

23
Carbene-catalyzed chemoselective reaction of unsymmetric enedials for access to Furo[2,3-b]pyrroles DOI Creative Commons
Guodong Fan,

Qingyun Wang,

Jun Xu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 15, 2023

Abstract A carbene-catalyzed chemoselective reaction of unsymmetric enedials is disclosed. The provides a concise access to bicyclic furo[2,3-b]pyrroles derivatives in excellent selectivity. main challenge this the two aldehyde moieties enedial substrates. Mechanistic studies via experiments suggest that our chemoselectivity controls are mostly achieved on reducing properties different sited Breslow intermediates. Several side reactions processes and corresponding adducts also studied by high resolution mass spectroscopy analysis. Our method allows for efficient assembly furo[2,3-b]pyrrole structural their analogues widely found natural products pharmaceuticals.

Language: Английский

Citations

12
Advancing Recyclable Thermosets through C═C/C═N Dynamic Covalent Metathesis Chemistry DOI
Jie Zheng,

Hongzhi Feng,

Xinglong Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21612 - 21622

Published: July 24, 2024

Thermoset polymers have become integral to our daily lives due their exceptional durability, making them feasible for a myriad of applications; however, this ubiquity also raises serious environmental concerns. Covalent adaptable networks (CANs) with dynamic covalent linkages that impart efficient reprocessability and recyclability thermosets garnered increasing attention. While various exchange reactions been explored in CANs, many rely on the stimuli active nucleophilic groups and/or catalysts, introducing performance instability escalating initial investment. Herein, we propose new direct catalyst-free C═C/C═N metathesis reaction between α-cyanocinnamate aldimine as novel motif constructing recyclable thermosets. This chemistry offers mild conditions (room temperature catalyst-free), ensuring high yields simple isolation procedures. By incorporating into covalently cross-linked polymer networks, obtained exhibit both malleability reconfigurability. The resulting tunable properties, coupled thermal stability linkage-based enrich toolbox chemistry.

Language: Английский

Citations

4
Redox reaction between N-heterocyclic carbenes and sulfonates: insights into unproductive catalytic paths DOI
Jia Song, Wei Wang, Guanjie Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This study provides new insights and understanding of the possible deactivation pathways NHC catalysts via uncommon redox processes with sulfonyl compounds, which should inspire future catalyst design reaction development.

Language: Английский

Citations

0