Copper‐Mediated Difluoromethylation of (Hetero)aryl Iodides and β‐Styryl Halides with Tributyl(difluoromethyl)stannane

Prakash, G. K. Surya; Ganesh, Sivagini; Jones, John Paul; Kulkarni, Aditya; Masood, Kamil; Swabeck, Joseph K.; Oláh, George A.

doi:10.1002/anie.201205850

Cited by 303 publications

(90 citation statements)

References 24 publications

(15 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Nevertheless, tedious protection/deprotection steps in these reactions significantly decreased the overall efficiency of the transformations. More recently, three copper-mediated direct difluoromethylation of aryl and vinyl iodides have been reported [20][21][22] . These transformations represent as a major step forward.…”

mentioning

confidence: 99%

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

2014

View full text Add to dashboard Cite

Difluoromethylated arenes are one of the privileged structural motifs that are important for fine tuning the biological properties of drug molecules. No general catalytic method exists for the formation of difluoromethylarenes. Previous methods for the preparation of difluoromethylarenes typically required harsh conditions, multiple steps or stoichiometric amount of catalysts. Here we report a cooperative dual palladium/silver catalyst system for direct difluoromethylation of aryl bromides and iodides under mild conditions. We develop the system by initial preparation of the putative intermediates in the dual-catalytic cycles, followed by studying the elemental steps to demonstrate the viability of the proposed cooperative catalytic cycle. The reaction is compatible with a variety of functional groups such as ester, amide, protected phenoxide, protected ketone, cyclopropyl, bromide and heteroaryl subunits such as pyrrole, benzothiazole, carbazole or pyridine.

show abstract

mentioning

confidence: 99%

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

2014

View full text Add to dashboard Cite

show abstract

“…[262] Amii et al berichteten über die kupferkatalysierte Kreuzkupplung von Arylhalogeniden mit Ethyltrimethylsilyldifluoracetat zu substituierten Difluormethylbenzoaten, die durch Verseifung und Decarboxylierung in Difluormethylarene überführt wurden. [264] [266] Difluormethylarene kçnnen auch durch nucleophile Desoxyfluorierung aromatischer Aldehyde mit Deoxo-Fluor synthetisiert werden. [264] [266] Difluormethylarene kçnnen auch durch nucleophile Desoxyfluorierung aromatischer Aldehyde mit Deoxo-Fluor synthetisiert werden.…”

Section: Elektrophile Difluormethylierung üBer Carbenzwischenstufenunclassified

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

2013

View full text Add to dashboard Cite

Die wichtigsten konzeptionellen Fortschritt auf dem Gebiet der Fluorierungen der letzten zehn Jahre wurden durch die Organo‐ und Übergangsmetallkatalyse ermöglicht. Die schwierigste Umwandlung ist weiterhin die Bildung der C‐F‐Stammbindung, was in erster Linie eine Folge der hohen Hydratationsenergie von Fluorid, starker Metall‐Fluor‐Bindungen und der hoch polarisierten Bindungen zu Fluor ist. Den meisten Fluorierungen fehlt es immer noch an Allgemeingültigkeit, Vorhersagbarkeit und Kosteneffizienz. Trotz der Einschränkungen sind fluorierte Verbindungen mit modernen Fluorierungsmethoden leichter zugänglich als je zuvor. Vor allem beginnen sich die modernen Methoden auf Forschungsgebiete auszuwirken, die keine großen Materialmengen benötigen, z. B. die Wirkstoffentwicklung und die Positronenemissionstomographie. Diese Entwicklungen werden in diesem Aufsatz zusammengefasst und vor dem Hintergrund konventioneller Fluorierungsmethoden diskutiert.

show abstract

“…In 2012, Prakash and co‐workers described the copper‐mediated difluoromethylation of (hetero)aryl and β‐styryl iodides 59 a – n using n Bu 3 SnCF 2 H in the presence of KF (Scheme ) 36. A broad range of iodoarenes, including iodoquinoline 59 j and iodopyridine 59 k , were readily converted into the corresponding CF 2 H‐substituted arenes 60 a – n in moderate to high yields and with a high tolerance towards various functional groups (aldehyde, ketone, ester, nitrile, chloride).…”

Section: Introduction Of Functionalized Fluorinated Building Blocks Omentioning

confidence: 99%

Recent Progress toward the Introduction of Functionalized Difluoromethylated Building Blocks onto C(sp²) and C(sp) Centers

Belhomme

Besset

Poisson

et al. 2015

Chemistry A European J

313

View full text Add to dashboard Cite

Fluorine chemistry is a field undergoing tremendous expansion. Although much attention has been paid to the introduction of the fluorine atom and the CF3 group, less interest has been devoted to the introduction of functionalized fluorinated building blocks, in sharp contrast with the high versatility of the fluorinated products. In this Minireview, the most relevant methods for the introduction of difluoromethylated building blocks are summarized. Access to difluoromethylated arenes, alkenes, and alkynes is highlighted and special attention is paid to explanation of the reaction mechanism.

show abstract

Copper‐Mediated Difluoromethylation of (Hetero)aryl Iodides and β‐Styryl Halides with Tributyl(difluoromethyl)stannane

Cited by 303 publications

References 24 publications

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

Recent Progress toward the Introduction of Functionalized Difluoromethylated Building Blocks onto C(sp²) and C(sp) Centers

Contact Info

Product

Resources

About

Copper‐Mediated Difluoromethylation of (Hetero)aryl Iodides and β‐Styryl Halides with Tributyl(difluoromethyl)stannane

Cited by 303 publications

References 24 publications

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

Cooperative dual palladium/silver catalyst for direct difluoromethylation of aryl bromides and iodides

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

Recent Progress toward the Introduction of Functionalized Difluoromethylated Building Blocks onto C(sp2) and C(sp) Centers

Contact Info

Product

Resources

About

Recent Progress toward the Introduction of Functionalized Difluoromethylated Building Blocks onto C(sp²) and C(sp) Centers