Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd‐Catalysed Cross‐Coupling Reactions between Organolithium Reagents and (Hetero)aryl Halides. Issue 6 (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 international edition. Volume 58:Issue 6(2019)
• Page Start: 1799
• Page End: 1802
• Publication Date: 2019-01-17
• Subjects: cross-coupling reactions -- deep eutectic solvents -- organolithium compounds -- sustainable chemistry -- water chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201812537
• Languages: English
• ISSNs: 1433-7851

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 : Just add salt ! Water with added NaCl was a very effective reaction medium for performing direct and fast (within 20 s) Pd‐catalysed cross‐coupling reactions between organolithiums and a variety of (hetero)aryl halides at room temperature and under air. Catalyst and water recyclability and reusability were added advantages of the proposed protocol.