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

Gabriele, Bartolo; Salerno, Giuseppe; Plastina, Pierluigi; Costa, Mirco; Crispini, Alessandra

doi:10.1002/adsc.200303151

Cited by 56 publications

(23 citation statements)

References 38 publications

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“…This methodology has been successfully applied to the direct synthesis of a variety of carbonylated heterocycles starting from terminal alkynes bearing a suitably placed nucleophilic group. [82][83][84][85][86][87][88]…”

Section: Oxidative Carbonylation Of Organoboronic Reagentsmentioning

confidence: 99%

Oxidative Carbonylation Reactions: Organometallic Compounds (RM) or Hydrocarbons (RH) as Nucleophiles

Liu¹,

Zhang²,

Lei³

2011

Angew Chem Int Ed

471

144

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Oxidative carbonylation reactions have attracted broad interest from both academia and industry in recent years. Enormous efforts have gone into the syntheses of carbonate and urea derivatives through the oxidative carbonylation of alcohols and amines. Very recently, organometallic reagents (R-M) and hydrocarbons(R-H) were directly employed as nucleophiles to construct a C-C bond in oxidative carbonylation reactions. This Minireview summarizes this novel type of oxidative carbonylation reaction.

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Section: Oxidative Carbonylation Of Organoboronic Reagentsmentioning

confidence: 99%

Oxidative Carbonylation Reactions: Organometallic Compounds (RM) or Hydrocarbons (RH) as Nucleophiles

Liu¹,

Zhang²,

Lei³

2011

Angew Chem Int Ed

471

144

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“…Die Methode wurde auf die direkte Synthese einer Vielzahl von carbonylierten Heterocyclen angewendet, deren Ausgangsverbindungen terminale Alkine mit einer geeignet platzierten nucleophilen Gruppe waren. [82][83][84][85][86][87][88] …”

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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“…The 1 H NMR spectra were recorded on a Bruker DRX 500 instrument (500.13 MHz) in DMSO d 6 with Me 4 Si as the inter nal standard. The UV spectra were measured on a Specord M 40 spectrometer in ethanol.…”

Section: Methodsmentioning

confidence: 99%

“…Certain furan 2(5H ) one (but 2 en 4 olide) deriva tives are known to act on enzymes 1,2 and possess bacteri cidal, fungicidal, 3,4 or antibacterial 5, 6 properties. A series of natural compounds (alkaloids, steroids, tetronic and ascorbic acids, pheromones, and fragrances) 7-13 contain ∆ 2 butenolide fragments.…”

mentioning

confidence: 99%

Synthesis of 4-amino-substituted but-2-en-4-olides

et al. 2005

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Previously unknown 4 amino derivatives of spiro annelated ∆ 2 butenolide were synthe sized by the addition of various amines at the activated triple bond of 4 hydroxy 2 alkynoic esters.Key words: methyl 3 (1 hydroxycyclohexyl)prop 2 ynoate, amines, but 2 en 4 olides, Michael reaction, spiro compounds, 1 oxaspiro[4.5]dec 3 en 2 ones.Certain furan 2(5H ) one (but 2 en 4 olide) deriva tives are known to act on enzymes 1,2 and possess bacteri cidal, fungicidal, 3,4 or antibacterial 5,6 properties. A series of natural compounds (alkaloids, steroids, tetronic and ascorbic acids, pheromones, and fragrances) 7-13 contain ∆ 2 butenolide fragments. Earlier, 14 we have developed a facile procedure for the synthesis of 4 aminofuran 2(5H ) ones spiro annelated at position 5, which are of interest as biologically active compounds and intermediates in the synthesis of natural compounds. 15-20 This procedure in volves the reaction of esters of 4 hydroxyalk 2 ynoic acid derivatives, in particular, of compound 1, with primary (2) and secondary (3) amines (Scheme 1). Under the reaction conditions, the initially formed linear Michael adducts 4 and 5 undergo cyclization to give the corre sponding furan 2(5H ) one derivatives 6 and 7.The aim of the present study was to examine the scope of application of this one pot procedure and to synthesize a series of amino derivatives of but 2 en 4 olides con taining pharmacophoric substituents in the amine com ponent. For this purpose, we studied the reactions of methyl (1 hydroxycyclohexyl)propiolate 1 with various amines 2a-z and 3a-z. The reactions were carried out in the absence of catalysts in dry diethyl ether or in a 2 : 1 diethyl ether-methanol mixture at 20-60 °C. The reac tions with salts of amines were performed by refluxing in methanol in the presence of sodium acetate. In most cases, the desired amino derivatives of but 2 en 4 olides 6 and 7 were isolated in high yields. As expected, the reaction rate depends on the structure of the starting amine, the num ber of substituents, and their size. Benzylic amines 2a-d and 3e,f,h are most reactive. Thus, their reactions pro ceed readily in diethyl ether at room temperature, and the corresponding products 6 and 7 were obtained in 61-78% yields (Tables 1 and 2). N Nucleophiles, which are com ponents of heterocycles, such as piperidine (3i-l,o), piperazine (3q,s,t), and some other heterocycles (3v,x), react under more drastic conditions. For example, reflux ing of (-) anabasine 3о in butanol selectively afforded (in 74% yield) ∆ 2 butenolide 7о containing a chiral center in the α position with the respect to the nitrogen atom ([α D ] 24 -198.70 (c 1.00, CHCl 3 )). It should be noted that the analogous reaction of anabasine with nitrile of (1 hydroxycyclohexyl)propiolic acid (EtOH, 40 °C) gave only linear adduct 9 instead of iminolactone 8. 21 Under the above mentioned conditions, both amino groups in 1,2 diaminopropane are involved in the reaction to give bislactone 10.The addition of benzoylhydrazine 2x occurs at the C≡C bond through the t...

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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

Cited by 56 publications

References 38 publications

Oxidative Carbonylation Reactions: Organometallic Compounds (RM) or Hydrocarbons (RH) as Nucleophiles

Oxidative Carbonylation Reactions: Organometallic Compounds (RM) or Hydrocarbons (RH) as Nucleophiles

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

Synthesis of 4-amino-substituted but-2-en-4-olides

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