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Water and Sodium Chloride: Essential Ingredients for Robust and Fast Pd‐Catalysed Cross‐Coupling Reactions between Organolithium Reagents and (Hetero)aryl Halides
Author(s) -
Dilauro Giuseppe,
Francesca Quivelli Andrea,
Vitale Paola,
Capriati Vito,
Perna Filippo Maria
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201812537
Subject(s) - protonolysis , aryl , chemistry , halide , reagent , catalysis , coupling reaction , chloride , palladium , combinatorial chemistry , sodium , organic chemistry , alkyl
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.