Visible-Light-Induced Acylative Pyridylation of Styrenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4727 - 4732

Published: May 29, 2024

A visible-light-induced photocatalyst-free acylative pyridylation of styrenes with 4-acyl-1,4-dihydropyridines (DHPs) and 4-cyanopyridines has been described, featuring mild reaction conditions, a broad substrate scope, good functional group tolerance. The could also be performed under sunlight irradiation albeit slightly lower conversion. 4-Acyl-1,4-DHPs serve dual role, acting as both photoreductant to reduce the cyanopyridine its radical anion intermediate precursor produce acyl radical. mechanism was especially elucidated through Hammett analysis, quadratic linear regression analysis by using parameters, σmb σjj·. findings from further demonstrate that rate-limiting step process is single electron transfer between 4-acyl-1,4-DHPs 4-cyanopyridines.

Language: Английский

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Site-Selective Pyridine Carbamoylation Enabled by Consecutive Photoinduced Electron Transfer

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 15521 - 15527

Published: Oct. 4, 2024

Language: Английский

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Visible-Light Photocatalytic Nucleophilic Addition of 4-Pyridylphosphonium Salts to CO₂ and Carbonyl Compounds

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

A visible-light photocatalytic nucleophilic addition of 4-pyridylphosphonium salts to CO2 and carbonyl compounds is reported. The reaction has mild conditions, good functional group tolerance, a wide range substrates. Mechanistic studies show that the may occur through pyridylphosphonium salt radical anion, pyridyl radical, anion intermediates. By combination with C4-H phosphination, this method can be applied late-stage C-H functionalization drugs containing pyridine unit.

Language: Английский

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High‐Energy Ball Milling Enables an Ultra‐fast Wittig Olefination Under Ambient and Solvent‐free Conditions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(49)

Published: Aug. 29, 2024

Abstract 30 Seconds to success!—The Wittig reaction, a fundamental and extensively utilized reaction in organic chemistry, enables the efficient conversion of carbonyl compounds olefins using phosphonium salts. Traditionally, meticulous setup, including pre‐formation reactive ylide species via deprotonation salt, is crucial for achieving high‐yielding reactions under classical solution‐based conditions. In this report, we present an unprecedented protocol ultra‐fast mechanically induced solvent‐free ambient conditions, often eliminating need tedious strict air moisture exclusion. A range aldehydes ketones were reacted with diverse salts high‐energy ball milling frequently giving access respective only seconds.

Language: Английский

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High‐Energy Ball Milling Enables an Ultra‐fast Wittig Olefination Under Ambient and Solvent‐free Conditions

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(49)

Published: Aug. 29, 2024

Abstract 30 Sekunden zum Erfolg! – Die Wittig‐Reaktion, eine grundlegende und weit verbreitete Reaktion in der organischen Synthesechemie, ermöglicht die effiziente Umwandlung von Carbonylverbindungen zu den entsprechenden Olefinen unter Verwendung Phosphoniumsalzen. Traditionell ist ein sorgfältiger Reaktionsaufbau, einschließlich vorangestellten Bildung einer reaktiven Ylid‐Spezies durch Deprotonierung eines Phosphoniumsalzes, entscheidend, um hohe Ausbeuten klassischen, lösungsmittelbasierten Bedingungen erzielen. In diesem Bericht stellen wir noch nie dagewesenes Protokoll für ultraschnelle mechanisch induzierte Wittig‐Reaktion lösungsmittelfreien vor, welches mühsame initiale Ylid‐Bildung striktem Luft‐ Feuchtigkeitsausschluss oft überflüssig macht. Eine Reihe Aldehyden Ketonen wurde mit verschiedenen Phosphoniumsalzen mittels hochenergetischem Kugelmahlen umgesetzt, wobei Olefine häufig nur zugänglich waren.

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