K2S2O8‐Mediated Access to Alkylsulfonated Spiro[4,5] Trienones from N‐Arylpropiolamides with the Insertion of Sulfur Dioxide DOI

Xin‐Qian Liu,

Peng‐Fei Huang, Biquan Xiong

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(3), P. 488 - 493

Published: Dec. 23, 2023

Abstract A four‐component reaction of N ‐arylpropiolamides, Hantzsch esters, Na 2 S O 5 and water via a radical cascade cyclization process with the insertion sulfur dioxide mediated by K 8 is reported. series alkylsulfonated spiro[4,5] trienones are prepared up to 86% yield good functional group tolerance substrate applicability. Preliminary mechanism experiments indicate that carbonyl oxygen originated from water.

Language: Английский

Copper-Catalyzed Chemoselective (Amino)fluorosulfonylation of Hydrocarbons via Intramolecular Fluorine-Atom Transfer DOI

Shuting Qu,

Xiao‐Xi Li, Xingwei Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4318 - 4328

Published: March 6, 2024

Sulfonyl fluorides have found increasing applications as functional molecules in chemistry and biology. We herein report a copper-catalyzed atom-economical access to two categories of sulfonyl through radical relay strategy the presence an SO2 surrogate. The aliphatic C(sp3)–H bond N-fluoro-N-alkyl sulfonamides reacted via 1,5-hydrogen atom transfer (HAT) process, affording alkanesulfonyl with proximal amino group. On other hand, utilizing substrates containing proper C═C double resulted intramolecular olefin aminofluorosulfonylation, allowing synthesis fluorosulfonyl-functionalized pyrrolidines piperidines atom-transfer addition (ATRA). Both reaction systems proceeded under mild conditions, requiring no additional fluorine source. Experimental computational studies suggest that S–F coupling is likely achieved radical-rebound pathway. By taking advantage SuFEx multifunctionality products, method applicable late-stage modification bioactive compounds, drug ligation chemistry, organic synthesis.

Language: Английский

Citations

11
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

10
Electrocatalytic Annulation–Iodosulfonylation of Indole‐Tethered 1,6‐Enynes to Access Pyrrolo[1,2‐a]indoles DOI

Ya‐Yu Yuan,

Xi Chen,

J. Wang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(10)

Published: Jan. 9, 2024

Abstract We present the first example of electrocatalytic three‐component annulation–iodosulfonylation indole‐tethered 1,6‐enynes with arylsulfonyl hydrazides and KI for accessing various iodosulfonated pyrrolo[1,2‐ a ]indoles in moderate to excellent yields high stereospecificity. This electrosynthesis opens new avenues construction skeleton good functional group compatibility under environmentally benign condition. Based on control experiments cyclic voltammetry data, we suggested plausible reaction mechanism which included anodic oxidation, homolysis iodide, radical addition, 5 ‐ exo dig cyclization, coupling or nucleophilic attack iodide ions cascade.

Language: Английский

Citations

8
Recent advancements in metal‐catalyst‐free multicomponent radical sulfonylation of alkynes DOI
Rongnan Yi, Qiang Li, Hongxin Liu

et al.

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

Published: June 4, 2024

Vinyl sulfones are crucial building blocks in synthetic chemistry and core structural units of pharmaceutically active molecules, thus extensive investigations have been conducted on the construction these skeletons. In contrast to classical approaches, radical sulfonylation alkynes for producing vinyl has garnered considerable interest because its mild conditions high efficiency. Radical sulfonation typically begins with sulfonyl attacking alkynes, followed by further functionalization. Moreover, association metal-catalyst-free systems multicomponent reactions (MCRs) offers an environmentally friendly pathway efficiently constructing complex scaffolds from readily available partners. However, there is no comprehensive review summarizing advancements alkynes. Hence, we provide a categorical overview based objects (hydrosulfonylation, carbosulfonylation, aminosulfonylation, oxysulfonylation, sulfosulfonylation, selenosulfonylation, iodosulfonylation), along interpretations reaction mechanisms.

Language: Английский

Citations

8
Oxidant-Assisted Sulfonylation/Cyclization Cascade Synthesis of Alkylsulfonylated Oxindoles via the Insertion of SO2 DOI
Long‐Jin Zhong, Hui Chen, Xuan Shang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5409 - 5422

Published: April 2, 2024

An oxidant-assisted tandem sulfonylation/cyclization of electron-deficient alkenes with 4-alkyl-substituted Hantzsch esters and Na2S2O5 for the preparation 3-alkylsulfonylated oxindoles under mild conditions in absence a photocatalyst transition metal catalyst is established. The mechanism studies show that alkyl radicals, which come from cleavage C–C bond 4-substituted oxidant conditions, subsequently undergo situ insertion sulfur dioxide to generate crucial alkylsulfonyl radical intermediates. This three-component reaction provides an efficient facile route construction alkylsulfonylated avoids use highly toxic chlorides or hydrazines as sources.

Language: Английский

Citations

5
Copper‐catalyzed radical‐induced annulation‐halo(bi)cyanomethylation of indole‐tethered 1,6‐enynes toward pyrrolo[1,2‐a]indoles DOI
Hang‐Dong Zuo,

Ya‐Yu Yuan,

Xi Chen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3578 - 3584

Published: June 18, 2024

Abstract A copper‐catalyzed radical‐induced annulation‐halocyanomethylation of indole‐linked 1,6‐enynes has been established using haloacetonitrile as radical precursors, enabling the synthesis 21 cyanomethylated pyrrolo[1,2‐ a ]indoles with yields ranging from 42% to 81% and Z / E ratio up 19:1. Moreover, by adjusting reaction temperature, variation annulation‐bromobicyanomethylation process was achieved, resulting in production 12 bicyanomethylated ]indole isomers 41–68%. The stereoisomeric mixture products could be purified their pure configurations through recrystallization. proposed mechanism formulated series control experiments.

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
DABCO‐Mediated Photoelectrochemical Three‐Component Sulfonocyclization of 3‐Aza‐1,5‐dienes DOI

Lu-Cai Ding,

Gui-Hong Yang,

Li Luo

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 2, 2024

Comprehensive Summary Herein, we report a rare example of three‐component net‐oxidative sulfonylation SO 2 surrogate with an oxidatively activated radical precursor under mild and metal‐ external‐oxidant‐free conditions. The mildness sustainability the reaction are enabled by photoelectrocatalysis, 3‐aza‐1,5‐dienes, organotrifluoroborates 1,4‐diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO) undergo sulfonylative cyclization to afford sulfono 4‐pyrrolin‐2‐ones in atom‐economical manner broad substrate scope good functional‐group tolerance. protocol is amenable late‐stage diversification complex molecular architectures as well gram‐scale synthesis. Sunlight could be used light source, conducted all‐solar mode using commercially available photovoltaic panel generate electricity situ . Mechanistic studies reveal that generated (DABCO), which was generally innocent previous reactions, functions electron shuttle between photocatalytic cycle reactants.

Language: Английский

Citations

2
K2S2O8‐Mediated Access to Alkylsulfonated Spiro[4,5] Trienones from N‐Arylpropiolamides with the Insertion of Sulfur Dioxide DOI

Xin‐Qian Liu,

Peng‐Fei Huang, Biquan Xiong

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(3), P. 488 - 493

Published: Dec. 23, 2023

Abstract A four‐component reaction of N ‐arylpropiolamides, Hantzsch esters, Na 2 S O 5 and water via a radical cascade cyclization process with the insertion sulfur dioxide mediated by K 8 is reported. series alkylsulfonated spiro[4,5] trienones are prepared up to 86% yield good functional group tolerance substrate applicability. Preliminary mechanism experiments indicate that carbonyl oxygen originated from water.

Language: Английский

Citations

5