Sulfenylcarbene-Mediated Carbon Atom Insertion for the Late-Stage Functionalization of N-Heterocycles

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 11, 2025

Late-stage functionalization (LSF) is a crucial strategy in drug discovery, allowing the modification of complex molecules, including pharmaceuticals, to enhance chemical diversity libraries. We harness chemoselectivity sulfenylcarbenes, which selectively react with alkenes even presence more reactive functional groups such as alcohols, carboxylic acids, and amines. This reactivity allows sulfenylcarbenes insert single carbon atom bearing diverse groups, transforming pyrroles, indoles, imidazoles into synthetically challenging pyridines, quinolines, pyrimidines, respectively. Sulfenylcarbene precursors are easily synthesized two steps from commercially available reagents. Our metal-free LSF approach employs benchtop-stable sulfenylcarbene enables late-stage natural products, amino C-glycosides. Mechanistic studies density theory (DFT) calculations were conducted investigate regio- outcomes.

Language: Английский

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CsCF3B(OMe)3: A Versatile Nucleophilic Source of the Trifluoromethyl Anion

Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Abstract We have identified cesium trimethoxy(trifluoromethyl)borate [CsCF3B(OMe)3] as a nucleophilic source for the trifluoromethylation of carbonyl compounds. A differentiating characteristic CsCF3B(OMe)3 is its heightened reactivity in ethereal solvents compared to potassium analogue, which typically employed dimethylformamide. Also, contrast extensively studied Ruppert–Prakash reagent (TMSCF3), does not require addition an exogenous activator. Described herein, we detail synthesis and demonstrate efficacy across various scaffolds, including methyl ketones, isatin derivatives, 1,2-acyclic dicarbonyls.

Language: Английский

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Amides Enable Room-Temperature CO₂ Conversion: Simple Organic Molecules Challenging Metal Catalysts

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

Published: Feb. 5, 2025

The conversion of carbon dioxide (CO2) into valuable chemicals has been intensively pursued for sustainable chemistry. It is highly desirable to achieve the under ambient conditions using organocatalysts instead precious or pollutive metal catalysts. Herein, we disclose a new class direct C(sp)-H carboxylation with CO2. Amide molecules such as N-methylacetamide and valerolactam behave efficient bifunctional catalysts promote aromatic alkynes propiolic acids. In particular, simple organic enable reaction occur at room temperature, which achieved only complex transition prior this report. presence optimal base Cs2CO3, adjacent nitrogen oxygen sites amide group concurrently activate CO2 position them in favor C-C coupling, affording high catalytic activity on par those work sheds light chemistry also illustrates great potential discovering from molecules.

Language: Английский

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“Cesium Effect”-Mediated/Controlled Divergent Synthesis via Synergistic Pd/Cu-Catalyzed Cascade Reactions

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8390 - 8402

Published: May 5, 2025

Language: Английский

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Cs₂CO₃-Catalyzed Rauhut–Currier-Type Reaction for the Synthesis of 2,3-Dihydrobenzo[b]oxepin Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16401 - 16405

Published: Oct. 29, 2024

The synthesis of fused benzoxepines relies on the use complex substrates and methodologies. Herein, we report our experimental theoretical findings about an unprecedented Rauhut-Currier-type reaction catalyzed by Cs

Language: Английский

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