Cascade C–H Activation/Annulation of Sulfoxonium Ylides with Vinyl Cyclopropanes: Access to Cyclopropane-Fused α-Tetralones DOI
Sharajit Saha, Bijoy Debnath, Kangkan Talukdar

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(19), P. 3352 - 3357

Published: May 4, 2023

Rh-catalyzed weak and traceless directing-group-assisted cascade C–H activation annulation of sulfoxonium ylides with vinyl cyclopropanes as a coupling partner have been accomplished to furnish functionalized cyclopropane-fused tetralones at moderate temperature. The C–C bond formation, cyclopropanation, functional group tolerance, late-stage diversifications drug molecules, scale-up are the important practical features.

Language: Английский

Transition-metal-free C–S bond cleavage and transformation of organosulfur compounds DOI
Ke Yang, Qin Li, Zhengyi Li

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(36), P. 5343 - 5364

Published: Jan. 1, 2023

The activation and transformation of organic chemical bonds is a fundamental scientific problem. In the past several decades, C-S bond cleavage for construction C-C C-heteroatom has received tremendous attention in chemistry. Although significant progress been made field transition metal strategies, variety novel transition-metal-free strategies have also developed using halogenated reagents, oxidants, acids, bases. Moreover, photochemical electrochemical methods to achieve organosulfur compounds. To date, however, no comprehensive review reported. Therefore, we herein provide major advances compounds, including thioethers, sulfoxides, sulfones, thioacetals, sulfonium salts, sulfur ylides.

Language: Английский

Citations

42
Photoredox-Catalyzed and Copper(II) Salt-Assisted Radical Addition/Hydroxylation Reaction of Alkenes, Sulfur Ylides, and Water DOI
Dongmei Yan,

Shuang-Hua Xu,

Hao Qian

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3279 - 3285

Published: Feb. 25, 2022

A visible light-driven photoredox-catalyzed and copper(II)-assisted three-component radical addition/hydroxylation reaction of alkenes, sulfur ylides, water is reported. This process shows broad substrate scope high functional group tolerance, with respect to both readily available ylides providing high-yielding practical access valuable γ-hydroxy carbonyl compounds. Key the success controlled generation α-carbonyl carbon radicals from via sulfonium salts by a visible-light-driven proton-coupled electron transfer (PCET) strategy in mixture 2,2,2-trifluoroethanol/CH2Cl2. Addition Cu(TFA)2·H2O helps accelerate radical-cation crossover improve efficiency. Mechanistic studies suggest that hydroxy moiety products stems water. study also builds up platform for further investigation into synthetic chemistry ylides.

Language: Английский

Citations

49
Ruthenium(ii)-catalyzed synthesis of CF3-isoquinolinones via C–H activation/annulation of benzoic acids and CF3-imidoyl sulfoxonium ylides DOI

Si Wen,

Yu‐Qing Zhang,

Qingyu Tian

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(16), P. 4388 - 4393

Published: Jan. 1, 2022

The synthesis of 3-trifluoromethylisoquinolinones by a ruthenium( ii )-catalyzed C–H activation/annulation reaction benzoic acids and CF 3 -imidoyl sulfoxonium ylides has been achieved.

Language: Английский

Citations

42
Visible-Light Photocatalyzed C3–H Alkylation of 2H-Indazoles/Indoles with Sulfoxonium Ylides via Diversified Mechanistic Pathways DOI
Altman Yuzhu Peng, Yujing Wang, Kaifeng Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(2), P. 1193 - 1204

Published: Jan. 9, 2024

Herein, the C3–H alkylation of 2H-indazoles and indoles with sulfoxonium ylides is developed under visible-light photocatalysis. This protocol employs easily accessible reagents, a wide range 2H-indazoles, indoles, are suitable for this reaction to afford desired products benign conditions. Synergistic experimental computational studies suggest that involving photocatalysis could proceed via different mechanistic pathways. For C3-alkylation triplet energy transfer pathway proposed quenching excited photocatalyst. Subsequently, formed state undergo radical attack on C═S moiety ylides. After dissociation DMSO 1,2-H migration, final product be yielded. However, such not applicable indoles. Instead, converted C-centered in presence KH2PO4 photoredox The can C3-site thus lead

Language: Английский

Citations

13
Continuous flow reactions in the preparation of active pharmaceutical ingredients and fine chemicals DOI
Guilherme M. Martins, Felipe C. Braga, Pedro P. de Castro

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(24), P. 3226 - 3239

Published: Jan. 1, 2024

This feature article presents an overview of continuous flow chemistry, including photoflow and electroflow technologies in the preparation active pharmaceutical ingredients (APIs) fine chemical intermediates.

Language: Английский

Citations

10
Visible Light-Promoted Regioselective Benzannulation of Vinyl Sulfoxonium Ylides with Ynoates DOI Creative Commons

Daksh Singh Davas,

Dinesh Kumar Gopalakrishnan,

Sandeep Kumar

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(3), P. 1073 - 1080

Published: March 1, 2024

Herein, we report a highly regioselective [4 + 2]-annulation of vinyl sulfoxonium ylides with ynoates under light-mediated conditions. The reaction proceeds through the new dienyl ylide, which undergoes photolysis blue light irradiation to give substituted naphthalene scaffolds. method presented here operates at room temperature and does not require addition an external photosensitizer. in situ-generated ylide absorbs acts as photosensitizer for formation arenes. synthetic potential these benzannulations was further illustrated by various transformations scale-up reaction. Moreover, control experiments quantum chemical calculations reveal mechanistic details developed

Language: Английский

Citations

9
Visible-light-induced organocatalytic enantioselective N–H insertion of α-diazoesters enabled by indirect free carbene capture DOI Creative Commons
Wengang Guo, Ying Zhou,

Hongling Xie

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 14(4), P. 843 - 848

Published: Nov. 29, 2022

While asymmetric insertion of metal carbenes into H-X (X = C, N, O, etc.) bonds has been well-established, control over free is challenging due to the presence strong background reactions and lack any anchor for a catalyst interaction. Here we have achieved first photo-induced metal-free bond this type. With visible light used as promoter chiral phosphoric acid catalyst, α-diazoesters aryl amines underwent smooth N-H form enantioenriched α-aminoesters with high efficiency good enantioselectivity under mild conditions. Key success was use DMSO an additive, which served rapidly capture highly reactive carbene intermediate domesticated sulfoxonium ylide.

Language: Английский

Citations

38
Diastereoselective Synthesis of Cyclopropanes from Carbon Pronucleophiles and Alkenes DOI Creative Commons
Min Ji Kim, Diana J. Wang, Karina Targos

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 16, 2023

Abstract Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes a limited array of substituents, difficult scale, or both. Herein, we disclose new cyclopropane synthesis through the formal coupling abundant carbon pronucleophiles unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis thianthrene presence substrates. We find that these dielectrophiles undergo methylene via alkenyl thianthrenium intermediates. protocol is scalable, proceeds high diastereoselectivity, tolerates diverse functional groups on both pronucleophile partners. To validate utility this procedure, prepared an substituted analogs established en route multiple pharmaceuticals.

Language: Английский

Citations

22
Divergent Synthesis of Tetrasubstituted Phenols via [3 + 3] Cycloaddition Reaction of Vinyl Sulfoxonnium Ylides with Cyclopropenones DOI
Shaoyong Chen, Yao‐Fu Zeng,

Wen‐Xuan Zou

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(23), P. 4286 - 4291

Published: June 2, 2023

Two categories of tetrasubstituted phenols were prepared via the cycloaddition reaction vinyl sulfoxonnium ylides with cyclopropenones in a switchable manner. Copper carbenoid was proposed as active intermediate process 2,3,4,5-tetrasubstituted formation, while 2,3,5,6-tetrasubstituted generated direct [3 + 3] annulation under metal-free conditions. Further synthetic applications also demonstrated.

Language: Английский

Citations

22
Insights into the multifaceted applications of vinyl sulfoxonium ylides DOI

Raju Sen,

Srashti Bhardwaj,

Krishnendu Bar

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(83), P. 12411 - 12422

Published: Jan. 1, 2023

Sulfoxonium ylides are important synthetic precursors in various organic transformations. Their potential was well explored the synthesis of bioactive natural products and pharmaceuticals. Vinyl sulfoxonium ylide is a stabilized containing an electron-deficient alkene at ylidic carbon. Similar to α-keto ylides, these reagents can generate vinyl carbenes presence metals under suitable conditions. These be used for transformations such as X-H (X = C, N, O, S) insertions, annulations, rearrangement reactions. Due dipole structure ylide, it undergo electrophilic addition with electrophiles α-position. synthons aromatic heteroaromatic compound syntheses. Moreover, their stability convenient handling make them replacements thermally less stable diazo compounds. Herein, we provide overview early efforts this area, particular emphasis on our own recent development ylide-mediated absence metal catalysis, also give personal perspectives challenges future scope improving application ylides.

Language: Английский

Citations

19