Transition-metal-free C–S bond cleavage and transformation of organosulfur compounds

Chemical Communications, Год журнала: 2023, Номер 59(36), С. 5343 - 5364

Опубликована: Янв. 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.

Язык: Английский

---

Asymmetric transformations from sulfoxonium ylides

Chemical Science, Год журнала: 2021, Номер 13(5), С. 1192 - 1209

Опубликована: Дек. 8, 2021

Sulfoxonium ylides are important surrogates for diazo compounds, and their use in industry as safer alternatives has been evaluated during recent years. Beyond the known classical transformations, these have also used a surprising plethora of novel intrinsic chemical reactions, especially Bench stability handling an advantage this class organosulfur molecules. Despite this, efficient asymmetric specifically catalytic enantioselective versions, only recently reported, there specific reasons this. This perspective article covers topic from first studies up to latest advances, giving personal perspectives showing main challenges area coming

Язык: Английский

---

Visible-Light Photocatalyzed C3–H Alkylation of 2H-Indazoles/Indoles with Sulfoxonium Ylides via Diversified Mechanistic Pathways

ACS Catalysis, Год журнала: 2024, Номер 14(2), С. 1193 - 1204

Опубликована: Янв. 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

Язык: Английский

---

Continuous flow reactions in the preparation of active pharmaceutical ingredients and fine chemicals

Chemical Communications, Год журнала: 2024, Номер 60(24), С. 3226 - 3239

Опубликована: Янв. 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.

Язык: Английский

---

Ruthenium-Catalyzed Chemoselective N–H Bond Insertion Reactions of 2-Pyridones/7-Azaindoles with Sulfoxonium Ylides

Organic Letters, Год журнала: 2021, Номер 23(3), С. 1038 - 1043

Опубликована: Янв. 21, 2021

A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, affording N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to achieve this unprecedented N–H rather than O–H insertion reaction is the use CpRu(PPh3)2Cl as catalyst sulfoxonium ylides alkylation reagents. Moreover, protocol also amenable 7-azaindoles by slightly varying conditions. Furthermore, sulfonium are suitable reagents, providing selectivity.

Язык: Английский

---

Visible-light-induced organocatalytic enantioselective N–H insertion of α-diazoesters enabled by indirect free carbene capture

Chemical Science, Год журнала: 2022, Номер 14(4), С. 843 - 848

Опубликована: Ноя. 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.

Язык: Английский

---

Rh(III)-Catalyzed Dual C–H Activation/Cascade Annulation of Benzimidates and CF₃-Imidoyl Sulfoxonium Ylides for the Synthesis of Trifluoromethyl-Decorated Benzo[de][1,8]naphthyridines

Organic Letters, Год журнала: 2022, Номер 24(48), С. 8864 - 8869

Опубликована: Дек. 1, 2022

An efficient and straightforward approach for the synthesis of trifluoromethyl-decorated benzo[de][1,8]naphthyridines has been achieved via Rh(III)-catalyzed dual C-H activation cascade annulation benzimidates CF3-imidoyl sulfoxonium ylides. The novel transformation involves formation four new chemical bonds along with release two molecules dimethyl sulfoxide (DMSO) one molecule each ethanol amine. optoelectronic properties obtained fused aromatic products have investigated by recording UV-vis absorption emission spectra.

Язык: Английский

---

Photo-Thermo-Mechanochemical Approach to Synthesize Quinolines via Addition/Cyclization of Sulfoxonium Ylides with 2-Vinylanilines Catalyzed by Iron(II) Phthalocyanine

Organic Letters, Год журнала: 2022, Номер 24(5), С. 1146 - 1151

Опубликована: Фев. 3, 2022

A novel photo-thermo-mechanochemical approach to assembling quinolines catalyzed by iron(II) phthalocyanine has been realized for the first time. This transformation features a cost-efficient catalytic system and operational simplicity, is free of solvent, shows good substrate tolerance, providing green alternative existing thermal approaches. Mechanistic experiments demonstrate that in-situ-formed secondary amine may be key intermediate further cyclization/aromatization process.

Язык: Английский

---

Insights into the multifaceted applications of vinyl sulfoxonium ylides

Chemical Communications, Год журнала: 2023, Номер 59(83), С. 12411 - 12422

Опубликована: Янв. 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.

Язык: Английский

---

Construction of α-Acyloxy Ketones via Photoredox-Catalyzed O–H Insertion of Sulfoxonium Ylides with Carboxylic Acids

Organic Letters, Год журнала: 2023, Номер 25(36), С. 6613 - 6617

Опубликована: Сен. 6, 2023

Herein, a photoredox-catalyzed insertion of sulfoxonium ylides with carboxylic acids was advanced under mild and simple conditions, offering practical approach for preparing α-acyloxy ketones broad scope acids. A combined experimental computational study suggests that this reaction proceeds via stepwise proton-assisted electron transfer mechanism.

Язык: Английский

---