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• W2037753722 abstract "Abstract The mechanism of the reaction of trans ‐ArPdBrL 2 (Ar= p ‐Z‐C 6 H 4 , Z=CN, H; L=PPh 3 ) with Ar′B(OH) 2 (Ar′= p ‐Z′‐C 6 H 4 , Z′=H, CN, MeO), which is a key step in the Suzuki–Miyaura process, has been established in N , N ‐dimethylformamide (DMF) with two bases, acetate ( n Bu 4 NOAc) or carbonate (Cs 2 CO 3 ) and compared with that of hydroxide ( n Bu 4 NOH), reported in our previous work. As anionic bases are inevitably introduced with a countercation M + (e.g., M + OH − ), the role of cations in the transmetalation/reductive elimination has been first investigated. Cations M + (Na + , Cs + , K + ) are not innocent since they induce an unexpected decelerating effect in the transmetalation via their complexation to the OH ligand in the reactive ArPd(OH)L 2 , partly inhibiting its transmetalation with Ar′B(OH) 2 . A decreasing reactivity order is observed when M + is associated with OH − : n Bu 4 N + > K + > Cs + > Na + . Acetates lead to the formation of trans ‐ArPd(OAc)L 2 , which does not undergo transmetalation with Ar′B(OH) 2 . This explains why acetates are not used as bases in Suzuki–Miyaura reactions that involve Ar′B(OH) 2 . Carbonates (Cs 2 CO 3 ) give rise to slower reactions than those performed from n Bu 4 NOH at the same concentration, even if the reactions are accelerated in the presence of water due to the generation of OH − . The mechanism of the reaction with carbonates is then similar to that established for n Bu 4 NOH, involving ArPd(OH)L 2 in the transmetalation with Ar′B(OH) 2 . Due to the low concentration of OH − generated from CO 3 2− in water, both transmetalation and reductive elimination result slower than those performed from n Bu 4 NOH at equal concentrations as Cs 2 CO 3 . Therefore, the overall reactivity is finely tuned by the concentration of the common base OH − and the ratio [OH − ]/[Ar′B(OH) 2 ]. Hence, the anionic base (pure OH − or OH − generated from CO 3 2− ) associated with its countercation (Na + , Cs + , K + ) plays four antagonist kinetic roles: acceleration of the transmetalation by formation of the reactive ArPd(OH)L 2 , acceleration of the reductive elimination, deceleration of the transmetalation by formation of unreactive Ar′B(OH) 3 − and by complexation of ArPd(OH)L 2 by M + ." @default.
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• W2037753722 date "2012-04-18" @default.
• W2037753722 modified "2023-10-18" @default.
• W2037753722 title "Mechanistic Origin of Antagonist Effects of Usual Anionic Bases (OH⁻, CO₃²⁻) as Modulated by their Countercations (Na⁺, Cs⁺, K⁺) in Palladium-Catalyzed Suzuki-Miyaura Reactions" @default.
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• W2037753722 doi "https://doi.org/10.1002/chem.201200516" @default.
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