Chemodivergent Csp ³ ─F bond functionalization and cross-electrophile alkyl-alkyl coupling with alkyl fluorides

Science Advances, Journal Year: 2022, Volume and Issue: 8(21)

Published: May 27, 2022

The widespread use of fluorinated organic compounds in the health, agrochemical, and materials sciences is sustained by a steadily growing pool commercially available fine chemicals. synthetic utility increasingly ubiquitous Csp 3 ─F bond, however, remains to be fully exploited, which often difficult task because its paramount stability chemical inertness. Here, we demonstrate chemodivergent activation monofluoroalkyl toward either nucleophilic or electrophilic intermediates. This accomplished under conditions that are compatible with several reaction types many functional groups, drastically widens current scope organofluorine chemistry sets stage for carbon-carbon carbon-heteroatom bond formations, stereoselective construction bisoxindole alkaloid scaffolds via situ Umpolung, cross-electrophilic coupling methodology. selective generation species possibility doing so simultaneously or, alternatively, switching molecular polarity enable previously unidentified opportunities recognize alkyl fluorides as building blocks.

Language: Английский

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Palladium-Catalyzed Cross-Electrophile Coupling between Aryl Diazonium Salt and Aryl Iodide/Diaryliodonium Salt in H₂O–EtOH

Organic Letters, Journal Year: 2023, Volume and Issue: 25(2), P. 341 - 346

Published: Jan. 6, 2023

We report herein a mild highly chemoselective palladium-catalyzed cross-electrophile coupling between readily accessible aromatic diazonium salt and aryl iodide or diaryliodonium in water-ethanol (2:1) medium. Mechanistic studies revealed that ethanol is crucial to generate an active Pd(0) catalyst, the counterion of renders cationic Pd(II) species facilitates subsequent oxidative addition iodide/diaryliodonium salt. Silver(I) was retain catalytic activity palladium, removing ion as precipitate.

Language: Английский

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C(sp²)–C(sp²) Reductive Cross-Coupling of Triarylphosphines with Aryl Halides by Palladium/Nickel Co-catalysis

Organic Letters, Journal Year: 2022, Volume and Issue: 24(30), P. 5573 - 5578

Published: July 21, 2022

Herein, we report the first general C(sp2)-C(sp2) reductive cross-coupling reaction of diverse triarylphosphines with a wide range aryl halides by palladium/nickel co-catalysis. This protocol offers unique route for synthesis biaryl compounds via activation inert C(Ar)-P bonds. The mechanistic studies demonstrate that formation phosphonium salts in situ plays key role catalytic cycle.

Language: Английский

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Nickel-Catalyzed Atroposelective Cross-Electrophile Coupling of Aryl Halides: A General and Practical Route to Diverse MOP-type Ligands

Published: April 4, 2024

We report a highly cross- and atroposelective coupling between ortho-(chloro)arylphosphine oxides ortho-(bromo)arylethers. This previously unknown asymmetric nickel-catalyzed reaction offers direct route to enantioenriched axially chiral biaryl monophos-phine that are difficult access by other means. These products can be readily reduced generate MOP-type ligands bear-ing complex skeletal backbones. The utility of these in catalysis is also demonstrated.

Language: Английский

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Ni/Photoredox-catalyzed coupling of aryl bromides and methylenecyclopropanes via selective distal bond cleavage

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5033 - 5043

Published: Jan. 1, 2024

A series of 1,1-dibenzylethylene derivatives were obtained in moderate-to-good yields via double coupling aryl bromides and methylenecyclopropanes Ni/photoredox catalysis. The critical roles nickel this reaction disclosed.

Language: Английский

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