It has always been a firm conviction of the scientific community that the employment of both anhydrous conditions and water-free reaction media is required for the successful handling of organometallic compounds with highly polarised metal–carbon bonds. Herein, we describe how, under heterogeneous conditions, Grignard and organolithium reagents can smoothly undergo nucleophilic additions to gchloroketones, on the way to 2,2-disubstituted tetrahydrofurans, “on water”, competitively with protonolysis, under batch conditions, at room temperature and under air. The reactivity of the above organometallic reagents has also been investigated in conventional anhydrous organic solvents and in bio-based eutectic and low melting mixtures for comparison. The scope and limitations of this kind of reaction are discussed.

Water opens the door to organolithiums and Grignard reagents: exploring and comparing the reactivity of highly polar organometallic compounds in unconventional reaction media towards the synthesis of tetrahydrofurans

CICCO, LUCIANA;MANSUETO, ROSMARA;PERNA, FILIPPO;Salomone, A;FLORIO, Saverio;CAPRIATI, Vito
2016-01-01

Abstract

It has always been a firm conviction of the scientific community that the employment of both anhydrous conditions and water-free reaction media is required for the successful handling of organometallic compounds with highly polarised metal–carbon bonds. Herein, we describe how, under heterogeneous conditions, Grignard and organolithium reagents can smoothly undergo nucleophilic additions to gchloroketones, on the way to 2,2-disubstituted tetrahydrofurans, “on water”, competitively with protonolysis, under batch conditions, at room temperature and under air. The reactivity of the above organometallic reagents has also been investigated in conventional anhydrous organic solvents and in bio-based eutectic and low melting mixtures for comparison. The scope and limitations of this kind of reaction are discussed.
File in questo prodotto:
File Dimensione Formato  
2016_Chem.Sci.pdf

accesso aperto

Tipologia: Documento in Versione Editoriale
Licenza: Creative commons
Dimensione 642.78 kB
Formato Adobe PDF
642.78 kB Adobe PDF Visualizza/Apri
2016_ChemSci_Synfact.pdf

non disponibili

Tipologia: Documento in Versione Editoriale
Licenza: NON PUBBLICO - Accesso privato/ristretto
Dimensione 456.32 kB
Formato Adobe PDF
456.32 kB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11586/144422
Citazioni
  • ???jsp.display-item.citation.pmc??? 13
  • Scopus 96
  • ???jsp.display-item.citation.isi??? 93
social impact