Synthesis of 2-ynamides by direct palladium-catalyzed oxidative aminocarbonylation of alk-1-ynes

Gabriele, Bartolo; Salerno, Giuseppe; Veltri, Lucia; Costa, Mirco

doi:10.1016/s0022-328x(00)00795-6

Cited by 81 publications

(47 citation statements)

References 16 publications

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“…Die erste katalytische Aminocarbonylierung von 1-Alkinen wurde von Gabriele et al [81] durchgeführt. Sowohl Alkylals auch Arylacetylene konnten erfolgreich zu den entsprechenden 2-Inamiden umgesetzt werden, wobei Arylacetylene die reaktiveren Substrate waren (Schema 19).…”

Section: 4oxidative Carbonylierung Von Organoborverbindungenunclassified

Oxidative Carbonylierungen: Organometallverbindungen (RM) oder Kohlenwasserstoffe (RH) als Nucleophile

2011

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Oxidative Carbonylierungen haben in den letzten Jahren ein breites Interesse geweckt, und insbesondere die Synthese von Carbonat‐ und Harnstoffderivaten durch oxidative Carbonylierung von Alkoholen und Aminen wurde intensiv untersucht. Eine neuartige Entwicklung ist die direkte Verwendung von Organometallverbindungen (RM) und Kohlenwasserstoffen (RH) als Nucleophile zum Aufbau einer C‐C‐Bindung in oxidativen Carbonylierungen. Dieser Kurzaufsatz stellt diese neue Art der oxidativen Carbonylierung vor.

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Section: 4oxidative Carbonylierung Von Organoborverbindungenunclassified

Oxidative Carbonylierungen: Organometallverbindungen (RM) oder Kohlenwasserstoffe (RH) als Nucleophile

2011

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“…(1). [1] 1 Reactions were carried out using a secondary dialkylamine as nucleophile (alkyne/amine molar ratio 1 : 1) in dioxane at 100 8C under 20 atm of a 4/1 mixture of CO/ air and were catalyzed by PdI 2 (0.2 mol %) in conjunction with KI (10 equiv. with respect to PdI 2 ).…”

Section: Introductionmentioning

confidence: 99%

“…[9] Results and Discussion 2-Methylbut-3-yn-2-ol 1a and morpholine 2a were first used as substrates. The reaction between 1a and 2a was initially carried out under conditions similar to those employed for the aminocarbonylation of 1-alkynes, [1] i.e., with PdI 2 in conjunction with KI as catalyst (PdI 2 /KI/ 1a/2a molar ratio 1 : 10 : 100 : 100) at 100 8C and under 16 atm of CO and 4 atm of air (20 atm total at 25 8C) in dioxane as the solvent (concentration of 1a 0.5 mmol/ mL of dioxane). After 15 h, a mixture of 5,5-dimethyl-4-morpholin-4-yl-5H-furan-2-one 3aa (13%), 4-hydroxy-4-methyl-1-morpholin-4-ylpent-2-ynone 4aa (36%), and (Z)-2-(1-hydroxy-1-methylethyl)-1,4-dimorpholin-4-ylbut-2-ene-1,4-dione 5aa (16%) was obtained at 100% substrate conversion [Eq.…”

mentioning

confidence: 99%

Expedient Synthesis of 4‐Dialkylamino‐5H‐furan‐2‐ones by One‐Pot Sequential Pd‐Catalyzed Oxidative Carbonylation of 2‐Yn‐1‐ols–Conjugate Addition‐Lactonization

et al. 2004

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A novel synthesis of 4-dialkylamino-5H-furan-2-ones 3 starting from very simple building blocks, i.e., a-substituted 2-yn-1-ols 1, carbon monoxide, dialkylamines 2 and oxygen is reported. Reactions are carried out in 1,2-dimethoxyethane at 100 8C and under 20 atm (at 25 8C) of a 4/1 mixture of CO/air in the presence of catalytic amounts of PdI 2 in conjunction with 10 equiv. of KI. Formation of 3 occurs through an ordered sequence of steps, namely (a) Pd-catalyzed oxidative monoaminocarbonylation of 1 to give 4-hydroxy-2-ynamides 4, which can be isolated under appropriate conditions; (b) stereoselective conjugate addition of 2 to the triple bond of 4, with formation of (not isolated) (E)-3-dialkylamino-4-hydroxy-2-enamides; (c) intramolecular alcoholysis of the amide function of the latter to give the final product 3.

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“…Under conditions similar to those optimized for 22, other 4-yn-1-ols (28) were selectively converted into the corresponding 2-[(methoxycarbonyl)methylene]tetrahydrofurans 29 in good isolated yields (around 60-70%) and excellent catalytic efficiencies (up to ca. 2300 mol of product per mol of catalyst, Equation 13).…”

Section: Equation 12mentioning

confidence: 99%

PdI₂-Catalyzed Synthesis of Heterocycles

Gabriele¹,

Salerno²,

Costa³

2004

Synlett

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Some PdI 2 -based complexes have proved to be efficient catalysts for the selective, atom-economical synthesis of different important heterocyclic derivatives starting from very simple building blocks, such as simple or functionalized alkynes, amino alcohols, diamines, carbon monoxide, carbon dioxide, alcohols, water, and oxygen. The synthetic protocols leading to heterocycles have been grouped into three classes of reactions: (a) cycloisomerization of (Z)-2-en-4-yn-1-ols, (Z)-2-en-4-yne-1-thiols, (Z)-(2-en-4ynyl)amines, 2-alkynylbenzyl alcohols to give substituted furans, thiophenes, pyrroles, and 1,3-dihydroisobenzofurans or 1H-isochromenes, respectively; (b) oxidative carbonylation of simple alkynes, 1,5-diynes, functionalized alkynes bearing a suitably placed nucleophilic group, amino alcohols, and diamines to afford substituted maleic anhydrides, functionalized b-and g-lactones, band g-lactams, dihydroindol-2-ones, furans, pyrroles, thiophenes, tetrahydrofurans, oxazolidin-2-ones, oxazolines, cyclic ureas, 4H-3,1-benzoxazines, quinazolin-2-ones, quinolin-4-ones; (c) reductive carbonylation of alkynes to give substituted g-lactones and formation of lactone or anhydride derivatives by additive carbonylation, resulting from the combination between oxidative carbonylation of the triple bond and reduction of a suitable functional group present in the substrate itself. Synthesis of Heterocycles by PdI 2 -Catalyzed Additive and Reductive Carbonylation Reactions 5.Conclusions

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Synthesis of 2-ynamides by direct palladium-catalyzed oxidative aminocarbonylation of alk-1-ynes

Cited by 81 publications

References 16 publications

Oxidative Carbonylierungen: Organometallverbindungen (RM) oder Kohlenwasserstoffe (RH) als Nucleophile

Oxidative Carbonylierungen: Organometallverbindungen (RM) oder Kohlenwasserstoffe (RH) als Nucleophile

Expedient Synthesis of 4‐Dialkylamino‐5H‐furan‐2‐ones by One‐Pot Sequential Pd‐Catalyzed Oxidative Carbonylation of 2‐Yn‐1‐ols–Conjugate Addition‐Lactonization

PdI₂-Catalyzed Synthesis of Heterocycles

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Synthesis of 2-ynamides by direct palladium-catalyzed oxidative aminocarbonylation of alk-1-ynes

Cited by 81 publications

References 16 publications

Oxidative Carbonylierungen: Organometallverbindungen (RM) oder Kohlenwasserstoffe (RH) als Nucleophile

Oxidative Carbonylierungen: Organometallverbindungen (RM) oder Kohlenwasserstoffe (RH) als Nucleophile

Expedient Synthesis of 4‐Dialkylamino‐5H‐furan‐2‐ones by One‐Pot Sequential Pd‐Catalyzed Oxidative Carbonylation of 2‐Yn‐1‐ols–Conjugate Addition‐Lactonization

PdI2-Catalyzed Synthesis of Heterocycles

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PdI₂-Catalyzed Synthesis of Heterocycles