Direct palladium-catalysed cross-couplings between organolithiums and (hetero)aryl halides (Br, Cl) proceed fast, cleanly and selectively at room temperature in air, with water as the only reaction medium and in the presence of NaCl as a cheap additive. Under optimised reaction conditions, a water-accelerated catalysis is responsible for furnishing Csp3–Csp2, Csp2–Csp2, and Csp–Csp2 cross-coupled products, competitively with protonolysis, within a 20 s reaction time, in yields of up to 99%, and in the absence of undesired dehalogenated/homocoupling side-products even if it starts from challenging secondary organolithiums. It is worth noting that the proposed protocol is scalable and the catalyst and water can easily and successfully be recycled up to 10 times, with an E-factor as low as 7.35.

Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd-catalysed Cross-coupling Reactions between Organolithiums and (Hetero)aryl halides

Giuseppe Dilauro;Andrea Francesca Quivelli;Paola Vitale;Vito Capriati
;
Filippo Maria Perna
2019-01-01

Abstract

Direct palladium-catalysed cross-couplings between organolithiums and (hetero)aryl halides (Br, Cl) proceed fast, cleanly and selectively at room temperature in air, with water as the only reaction medium and in the presence of NaCl as a cheap additive. Under optimised reaction conditions, a water-accelerated catalysis is responsible for furnishing Csp3–Csp2, Csp2–Csp2, and Csp–Csp2 cross-coupled products, competitively with protonolysis, within a 20 s reaction time, in yields of up to 99%, and in the absence of undesired dehalogenated/homocoupling side-products even if it starts from challenging secondary organolithiums. It is worth noting that the proposed protocol is scalable and the catalyst and water can easily and successfully be recycled up to 10 times, with an E-factor as low as 7.35.
File in questo prodotto:
File Dimensione Formato  
Dilauro_et_al-2019-Angewandte_Chemie_International_Edition.pdf

non disponibili

Descrizione: Articolo principale
Tipologia: Documento in Versione Editoriale
Licenza: NON PUBBLICO - Accesso privato/ristretto
Dimensione 626.3 kB
Formato Adobe PDF
626.3 kB Adobe PDF   Visualizza/Apri   Richiedi una copia
L-2019_ACIE Cross-coupling RLi_accepted.pdf

Open Access dal 19/01/2020

Descrizione: Articolo post print accesso pubblico
Tipologia: Documento in Post-print
Licenza: Creative commons
Dimensione 3.23 MB
Formato Adobe PDF
3.23 MB Adobe PDF Visualizza/Apri

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/11586/224319
Citazioni
  • ???jsp.display-item.citation.pmc??? 7
  • Scopus 55
  • ???jsp.display-item.citation.isi??? 49
social impact