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

Asymmetric Sulfonylation from a Reaction of Cyclopropan-1-ol, Sulfur Dioxide, and 1-(Alkynyl)naphthalen-2-ol DOI
Chun Zhang, Shengqing Ye, Jie Wu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3321 - 3325

Published: April 10, 2024

Asymmetric sulfonylation from a reaction of cyclopropan-1-ol, sulfur dioxide, and 1-(alkynyl)naphthalen-2-ol in the presence catalytic amount organocatalyst at room temperature is developed. Axially chiral (S)-(E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols are generated moderate to good yields with excellent enantioselectivity regioselectivity under mild conditions. During this transformation, γ-keto sulfinate situ cyclopropan-1-ol dioxide acts as key intermediate.

Language: Английский

Citations

8
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
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
A radical Smiles rearrangement difunctionalization of activated alkenes via desulfonylation and insertion of sulfur dioxide relay strategy DOI

Si‐Wei Tian,

Zhentao Luo,

Biquan Xiong

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(11), P. 6774 - 6778

Published: Jan. 1, 2024

A novel and attractive photochemical difunctionalization of N -tosyl acrylamide for constructing alkylsulfonylated oxindoles amides with excellent substrate adaptability via a radical Smiles rearrangement strategy is described.

Language: Английский

Citations

7
Oxidative sulfonylarylation of strained C–C σ-bonds for the synthesis of 3-spirocyclic oxindoles initiated by insertion of sulfur dioxide DOI
Jian-Hong Fan, Jing Yuan, Long‐Jin Zhong

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 1982 - 1989

Published: Jan. 1, 2024

Sulfonylarylation of bicyclobutyl N -aryl amides via radical cascade cyclization for constructing 3-spirocyclic oxindoles has been disclosed.

Language: Английский

Citations

6
Generation of Sulfamoyl Radical for the Modular Synthesis of Sulfonamides DOI

Haiping Lv,

Xinzhou Chen, Xuemei Zhang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6513 - 6524

Published: April 13, 2024

Efficient synthesis of sulfonamides has long been pursued by chemists due to their frequent occurrence in pharmaceuticals, especially anti-inflammatory medicines. The traditional assembly from sulfonyl chlorides and amines, as well the recently developed one-step involving sulfur dioxide, still faces challenges such poor substrate compatibility and/or stringent reaction conditions. Herein, we present a strategy for situ generation sulfamoyl radicals modular both alkenyl alkyl with wide applicability (>100 examples), mild conditions, easily accessible starting materials. This method is successfully applied late-stage modification drug molecules (23 molecule naratriptan, 15N-labeling sulfonamides.

Language: Английский

Citations

5
SO2-Insertion induced enantioselective oxysulfonylation to access β-chiral sulfones with quaternary carbon stereocenters DOI
Jun Zhang,

Xuefeng Wang,

Peiqi Wang

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(3), P. 908 - 913

Published: Dec. 5, 2023

Language: Английский

Citations

11
Recent advances in the palladium-catalyzed sulfonylation via SO2 insertion DOI
Yujiao Zhang,

Meng-Ling Li,

Haixia Hu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(29), P. 5868 - 5885

Published: Jan. 1, 2024

The importance of sulfonyl-group-containing compounds, such as sulfonamides, sulfones, sulfinate esters, and sulfonyl fluorides, in pharmaceuticals, bioactive molecules, natural products cannot be overstated. new development palladium-catalyzed sulfonylation

Language: Английский

Citations

4
Photocatalytic Three-Component Radical Sulfonarylation of Alkenes: Preparation of γ-Keto-Sulfone-Substituted Oxindoles DOI
Fei Chen,

Jun-Ya Guo,

Yunhong Jia

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 16, 2025

A photocatalytic radical sulfonarylation of N-arylacrylamides via a three-component cascade cyclopropyl alcohol ring opening/sulfur dioxide insertion/sulfonyl addition/cyclization sequence has been developed. This method employs alcohols as the precursors β-carbonyl alkyl radicals and Na2S2O5 cheap source sulfur dioxide. By using this procedure, wide variety γ-keto-sulfone-substituted oxindoles were facilely synthesized.

Language: Английский

Citations

0
Synthesis of Ester-Substituted Polycyclic N-Heteroaromatics via Photocatalyzed Alkoxycarbonylation/Tricyclization Reactions of Enediyne in Continuous Flow Conditions DOI
Shanshan Zhu, Zhiwei Chen, Dandan Fan

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

For the first time, a photoredox-catalyzed alkoxycarbonylation/tricyclization reaction was developed by employing readily accessible enediynes and alkyloxalyl chlorides as starting materials, enabling synthesis of ester-substituted polycyclic N-heteroaromatics under mild conditions through radical-mediated mechanism. This photocatalytic strategy is notable for its exceptional compatibility with diverse functional groups, scalability, efficiency in formation rings chemical bonds. Notably, continuous flow photocatalysis technology markedly improved these reactions compared to equivalent batch reactions, efficiently decreasing times merely 40 min.

Language: Английский

Citations

0