Expeditious Synthesis of Spiroindoline Derivatives via Tandem C(sp²)–H and C(sp³)–H Bond Functionalization of N-Methyl-N-nitrosoanilines

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3091 - 3096

Опубликована: Апрель 3, 2024

Presented herein is a novel synthesis of pharmaceutically privileged spiroindoline derivatives via cascade reactions N-methyl-N-nitrosoanilines with diazo homophthalimides. A group mechanistic studies disclosed that the formation product involves an unusual reaction mode N-methyl-N-nitrosoaniline featuring initial C(sp2)–H bond activation/alkylation followed by C(sp3)–H activation/spiroannulation. To our knowledge, this first example in which acts as C3N1 synthon to accomplish formal [4+1] spiroannulation participation N-methyl unit rather than previously reported C2N1 undergo [3+2] annulation without unit. In general, newly developed synthetic protocol features simple and readily accessible starting materials, valuable products, unique mechanism, high efficiency atom-economy, excellent compatibility diverse functional groups, ready scalability.

Язык: Английский

---

Pd-catalyzed regioselective activation of C(sp²)–H and C(sp³)–H bonds

Chemical Society Reviews, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Differentiating between two highly similar C-H bonds in a given molecule remains fundamental challenge synthetic organic chemistry. Directing group assisted strategies for the functionalisation of proximal has been known last few decades. However, distal bond is strenuous and requires distinctly specialised techniques. In this review, we summarise advancement Pd-catalysed C(sp

Язык: Английский

---

Synthesis of Heptacyclic Compounds through C–H Bond Activation-Initiated Cascade Reactions

Organic Letters, Год журнала: 2024, Номер 26(35), С. 7425 - 7430

Опубликована: Авг. 22, 2024

Presented herein is an atom- and step-economical method enabling the precise assembly of a heptacyclic scaffold containing both azocine indoline units through cascade reactions indolin-1-yl(aryl)methanimines with diazo indanediones. The formation products involves C–H bond activation double carbene insertion followed by intramolecular condensation, retro-[2 + 2] cycloaddition, recyclization. This reaction not only provided concise straightforward strategy for synthesis otherwise difficult to obtain compounds from readily available substrates but also disclosed unprecedented mode derivatives compounds. In general, this novel synthetic protocol has advantages, such as easily obtainable substrates, structurally sophisticated products, procedure, good compatibility diverse functional groups, ready scalability. Moreover, thus obtained showed decent antiproliferative activity against three human cancer cell lines.

Язык: Английский

---

Meta‐Selective Copper‐Catalyzed C−H Arylation of Pyridines and Isoquinolines through Dearomatized Intermediates

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 18, 2024

C(sp

Язык: Английский

---

Synthesis of Indenone-Fused Pyran Derivatives from Aryl Enaminones and Cyclopropenones through Unsymmetrical Relay C–H Bond Activation and Double C–C/C–O Bond Formation

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6602 - 6607

Опубликована: Июль 30, 2024

Presented herein is a novel synthesis of indenone-fused pyran derivatives via the cascade reactions aryl enaminones with cyclopropenones. The formation products involves one-pot procedure consisting C–H bond and enamine functionalization along C–C cleavage cyclopropenone 1,3-rearrangement in situ-formed allylic alcohol moiety followed by intramolecular O-nucleophilic addition Me2NH elimination. To our knowledge, this first simultaneous both indenone scaffolds through concurrent unsymmetrical relay activation double C–C/C–O formation. Moreover, usefulness method further showcased its suitability for large-scale synthetic scenarios diverse transformations products.

Язык: Английский

---

Visible-Light Photoredox-Catalyzed Direct Carboxylation of Tertiary C(sp³)–H Bonds with CO₂: Facile Synthesis of All-Carbon Quaternary Carboxylic Acids

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Окт. 7, 2024

Direct carboxylation of C–H bonds with CO2 represents an attractive strategy to synthesize valuable carboxylic acids high atom, step, and redox economy. Although great progress has been achieved in this field, catalytic tertiary C(sp3)–H still remains challenging due their inherent inertness significant steric hindrance. Herein, we report a direct benzylic via visible-light photoredox catalysis. Various all-carbon quaternary acids, which are importance medicinal chemistry, successfully obtained yields. This is characterized by good functional group tolerance, broad substrate scope, mild operational conditions. Furthermore, our methodology enables the efficient rapid synthesis key drug or bioactive molecules, such as carbetapentane, caramiphen, PRE-084 (σ1 receptor agonist), facilitates various functionalizations C(sp2)–H using directing ability target thus highlighting its practical applications. Mechanistic studies indicate that carbanion, serves intermediate react CO2, catalytically generated single electron reduction radical through consecutive photoinduced transfer process.

Язык: Английский

---

Synthesis of CF₃-Azafluorenes through the Cascade Reaction of 2H-Imidazoles with CF₃-Ynones

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 25, 2024

A concise synthesis of trifluoromethyl (CF

Язык: Английский

---

2-Pyridone-Directed Cu^II–Catalyzed General Method of C(sp²)-H Activation for C–S, C–Se, and C–N Cross-Coupling: Easy Access to Aryl Thioethers, Selenide Ethers, and Sulfonamides and DFT Study

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(10), С. 6798 - 6812

Опубликована: Апрель 25, 2024

We have demonstrated N-substituted 2-pyridones as an N,O-directing group for selective C(sp2)-H-activated thiolation, selenylation, and sulfonamidation of ortho C–H bonds benzamides. This method utilizes a cost-effective Cu(II)-salt catalyst instead precious metal catalysts, achieving high yields, including gram-scale synthesis excellent functional tolerance. applied this protocol to access 30 different compounds with demonstrating thiolation fluorine-substituted benzamides well. Density theory (DFT) calculations support the mechanism, acetate-supported concerted metalation deprotonation (CMD) steps unique role dimethyl sulfoxide (DMSO) solvent. The facile pharmaceutically important sulfonamides other highlights method's potential in chemistry medicinal chemistry.

Язык: Английский

---

Palladium-Catalyzed Solvent-Controlled Divergent C2/C5 Site-Selective Alkynylation of Pyrrole Derivatives

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Among the known aromatic

Язык: Английский

---

Palladium (II)/Lewis Acid Catalyzed Oxidative Olefination of 2-Benzamidopyridine 1-Oxide with Acrylates: Synthesis of Isoindolinones

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This work describes the development of a heterobimetallic Pd( ii )/Cu( )-catalyzed C–H olefination 2-benzamidopyridine 1-oxide with acrylates followed by intramolecular aza-Michael addition to construct desired isoindolinone core.

Язык: Английский

---