Nickel(0)-induzierte kupplung von benzaldehyd mit isocyanaten zu nickela-heterocyclen

Hoberg, Heinz; Sümmermann, Klaus

doi:10.1016/0022-328x(84)85082-2

Cited by 21 publications

(8 citation statements)

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“…In addition, isocyanates have been shown to react on nickel(0) with electronically activated alkenes, 6 1,3-dienes, 7 allenes, 8 and aldehydes. 9 Most recently, Louie has demonstrated that an NHC-nickel(0) system efficiently catalyzes the cycloaddition of diynes or alkynes and isocyanates to form pyridones. 10a Cycloadditions run with an excess of isocyanate lead to the formation of pyrimidinediones.…”

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confidence: 99%

Nickel-Catalyzed Synthesis of Acrylamides from α-Olefins and Isocyanates

Schleicher

Jamison

2007

Org. Lett.

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The nickel(0)-catalyzed coupling of α-olefins and isocyanates proceeds in the presence of the Nheterocyclic carbene ligand IPr to provide α,β-unsaturated amides. Carbon-carbon bond formation occurs preferentially at the 2-position of the olefin. The N-tert-butyl amide products can be converted to the corresponding primary amides under acidic conditions. A major goal of organic chemistry is the elaboration of molecular complexity from simple, inexpensive precursors. Catalytic reactions that effect selective carbon-carbon bond formation facilitate this aim with economy of operations 1 and materials. 2 Methodology for the selective coupling of α-olefins and isocyanates to provide acrylamides has potential applications in the field of polymer science. Poly(N-alkylacrylamide)s and poly(N-alkylmethacrylamide)s have been extensively studied for their properties as temperature-sensitive aqueous microgels. 3 The monomers are commonly prepared by reaction of (meth)acryloyl chloride with the corresponding amine. By comparison, direct synthesis of these unsaturated amides from alkenes and isocyanates would afford monomers with a greater variety of substitution patterns of the polymer backbone and avoid the formation of byproducts such as chloride salts. 4 Several nickel(0)-mediated reactions of isocyanates have been described in the literature. Much of the seminal investigation in this area was done by Hoberg, who first reported the stoichiometric 5a and catalytic 5c coupling reactions of phenyl isocyanate and ethylene on nickel(0) with trialkyl phosphine ligands to give N-phenyl acrylamide. Hoberg proposed that the reaction proceeds via an azanickelacyclopentanone intermediate, which then undergoes β-hydrogen elimination (Scheme 1).Other α-olefins react with phenyl isocyanate with nickel(0) and phosphine ligands; 5b,d-h the major product is the trans-disubstituted α,β-unsaturated amide. Formation of a 1,1-disubstituted acrylamide is observed only in two cases as a minor product, in 3% and 13%

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Nickel-Catalyzed Synthesis of Acrylamides from α-Olefins and Isocyanates

Schleicher

Jamison

2007

Org. Lett.

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“…Mit Diphenylacetylen reagiert 1 unter 1,2-Addition zum ockerfarbenen Vinylkomplex 6 erhitzt, so kann nach hydrolytischer Aufarbeitung das Acrylslureanilid 6 in 90% Ausbeute (bezogen auf 3) isoliert werden.…”

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CC‐Verknüpfung von Alkenen mit Isocyanaten an Ni⁰‐Komplexen – eine neue Synthese von Acrylsäureamiden

1985

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“…D arüber hinaus können an bestim mten (Lig)Ni"-Systemen auch Isocyanate mit ungesättigten Substra ten, wie Iminen oder A ldehyden, im Zuge einer 1/1-Kupplung zu Diazanickelacyclopentanonen (1) [8] bzw. O xazanickelacyclopentanonen (2) [9] verknüpft werden. Zur Erm ittlung der katalytischen Aktivität wurde, um vergleichbare, aussagekräftige Ergebnisse zu e r halten, unter den in Lit.…”

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“…10 kann mit im Ü ber schuß vorhandenem Aldehyd unter C -C-Verknüp-fung zu dem Komplex 11 (Lig = Dipy [13,14]) ab reagieren. D er Kupplungsschritt 1 0^2 ist für Lig = T M E D A belegt [9]. Die im Schema aufgeführten Nickelkomplexe 8, 9 und 11 führen im Katalysecyclus zum Reaktionsabbruch.…”

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Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes

Hoberg

Sümmermann

1984

Zeitschrift Für Naturforschung B

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Nickel(0)-induzierte kupplung von benzaldehyd mit isocyanaten zu nickela-heterocyclen

Cited by 21 publications

References 20 publications

Nickel-Catalyzed Synthesis of Acrylamides from α-Olefins and Isocyanates

Nickel-Catalyzed Synthesis of Acrylamides from α-Olefins and Isocyanates

CC‐Verknüpfung von Alkenen mit Isocyanaten an Ni⁰‐Komplexen – eine neue Synthese von Acrylsäureamiden

Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes

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Nickel(0)-induzierte kupplung von benzaldehyd mit isocyanaten zu nickela-heterocyclen

Cited by 21 publications

References 20 publications

Nickel-Catalyzed Synthesis of Acrylamides from α-Olefins and Isocyanates

Nickel-Catalyzed Synthesis of Acrylamides from α-Olefins and Isocyanates

CC‐Verknüpfung von Alkenen mit Isocyanaten an Ni0‐Komplexen – eine neue Synthese von Acrylsäureamiden

Nickel(0)-katalysierte Synthese von Iminen aus Isocyanaten und Aldehyden/ Nickel(0) Catalysed Synthesis of Imines from Isocyanates and Aldehydes

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CC‐Verknüpfung von Alkenen mit Isocyanaten an Ni⁰‐Komplexen – eine neue Synthese von Acrylsäureamiden