Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd‐Catalysed Cross‐Coupling Reactions between Organolithium Reagents and (Hetero)aryl Halides. (17th January 2019)

• Record Type: Journal Article
• Authors: Dilauro, Giuseppe; Francesca Quivelli, Andrea; Vitale, Paola; Capriati, Vito; Perna, Filippo Maria
• Is Part Of: Angewandte Chemie. Volume 131:Number 6(2019)
• Page Start: 1813
• Page End: 1816
• Publication Date: 2019-01-17
• Subjects: Kreuzkupplungen -- Nachhaltige Chemie -- Organolithiumverbindungen -- Tiefschmelzende Eutektika -- Wasser; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201812537
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Direct palladium‐catalysed cross‐couplings between organolithium reagents 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 C(sp 3 )–C(sp 2 ), C(sp 2 )–C(sp 2 ), and C(sp)–C(sp 2 ) cross‐coupled products, in competition with protonolysis, within a reaction time of 20 s, in yields of up to 99 %, and in the absence of undesired dehalogenated/homocoupling side products even when challenging secondary organolithiums serve as the starting material. 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. Abstract : Einfach Salz zugeben ! Wasser mit NaCl‐Zusatz ist ein hocheffektives Reaktionsmedium für schnelle (20 s) und direkte Pd‐katalysierte Kreuzkupplungen zwischen Organolithiumspezies und vielfältigen (Hetero)Arylhalogeniden bei Raumtemperatur und an Luft. Katalysator und Wasser sind bei diesem Protokoll wiederverwendbar.