The straightforward in situ synthesized bis(2,6-diisopropyl)acenaphthenequinonediimine palladium triflate catalyst was generally employed for both the mono-alkoxycarbonylation of terminal alkynes, and the bis-alkoxycarbonylation of 1,2-disubstituted alkynes by using mild reaction conditions [carbon monoxide pressure (PCO)=4 bar, temperature=20 °C]. Utilizing low catalyst loading (down to 0.5 mol%), a variety of propiolic esters were synthesized with good to excellent isolated yields. Most importantly the system was very efficient not only with methanol but also with a range of different alcohols, starting from the less hindered benzyl alcohol to the most hindered ones, such as isopropyl alcohol and tert-butyl alcohol. In addition, aromatic and aliphatic 1,2-disubstituted alkynes were converted into maleic acid derivatives, together with an acid-catalyzed isomerization reaction, showing modest to good selectivity and excellent combined yields. In particular 3-hexyne showed a satisfactory degree of selectivity for the maleic diesters of methanol and benzyl alcohol, obtaining the corresponding products with good isolated yields. (Figure presented.).

Oxidative Alkoxycarbonylation of Alkynes by Means of Aryl alpha-Diimine Palladium(II) Complexes as Catalysts / Beltrani, Michela; Carfagna, Carla; Milani, Barbara; Mancuso, Raffaella; Gabriele, Bartolo; Fini, Francesco. - In: ADVANCED SYNTHESIS & CATALYSIS. - ISSN 1615-4150. - ELETTRONICO. - 358:20(2016), pp. 3244-3253. [10.1002/adsc.201600521]

Oxidative Alkoxycarbonylation of Alkynes by Means of Aryl alpha-Diimine Palladium(II) Complexes as Catalysts

FINI, Francesco
2016

Abstract

The straightforward in situ synthesized bis(2,6-diisopropyl)acenaphthenequinonediimine palladium triflate catalyst was generally employed for both the mono-alkoxycarbonylation of terminal alkynes, and the bis-alkoxycarbonylation of 1,2-disubstituted alkynes by using mild reaction conditions [carbon monoxide pressure (PCO)=4 bar, temperature=20 °C]. Utilizing low catalyst loading (down to 0.5 mol%), a variety of propiolic esters were synthesized with good to excellent isolated yields. Most importantly the system was very efficient not only with methanol but also with a range of different alcohols, starting from the less hindered benzyl alcohol to the most hindered ones, such as isopropyl alcohol and tert-butyl alcohol. In addition, aromatic and aliphatic 1,2-disubstituted alkynes were converted into maleic acid derivatives, together with an acid-catalyzed isomerization reaction, showing modest to good selectivity and excellent combined yields. In particular 3-hexyne showed a satisfactory degree of selectivity for the maleic diesters of methanol and benzyl alcohol, obtaining the corresponding products with good isolated yields. (Figure presented.).
31-ago-2016
358
20
3244
3253
Oxidative Alkoxycarbonylation of Alkynes by Means of Aryl alpha-Diimine Palladium(II) Complexes as Catalysts / Beltrani, Michela; Carfagna, Carla; Milani, Barbara; Mancuso, Raffaella; Gabriele, Bartolo; Fini, Francesco. - In: ADVANCED SYNTHESIS & CATALYSIS. - ISSN 1615-4150. - ELETTRONICO. - 358:20(2016), pp. 3244-3253. [10.1002/adsc.201600521]
Beltrani, Michela; Carfagna, Carla; Milani, Barbara; Mancuso, Raffaella; Gabriele, Bartolo; Fini, Francesco
File in questo prodotto:
File Dimensione Formato  
31 - Adv. Synth. Catal. 2016 Beltrani 3244-3253.pdf

non disponibili

Descrizione: Articolo Principale
Tipologia: Versione dell'editore (versione pubblicata)
Dimensione 552.74 kB
Formato Adobe PDF
552.74 kB Adobe PDF   Visualizza/Apri   Richiedi una copia
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1123856
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 14
  • ???jsp.display-item.citation.isi??? 13
social impact