Copper-Free Halodediazoniation of Arenediazonium Tetrafluoroborates in Deep Eutectic Solvents-like Mixtures

Abstract

Deep Eutectic Solvent (DES)-like mixtures, based on glycerol and different halide organic and inorganic salts, are successfully exploited as new media in copper-free halodediazoniation of arenediazonium salts. The reactions are carried out in absence of metal-based catalysts, at room temperature and in a short time. Pure target products are obtained without the need for chromatographic separation. The solvents are fully characterized, and a computational study is presented aiming to understand the reaction mechanism.

Temperature-induced formation of Pd nanoparticles in heterogeneous nanobiohybrids: application in C–H activation catalysis

“…It has been reported that these mechanisms prevail when arenediazonium salts are used as electrophilic reagents in Cu( i )-assisted nucleophilic substitution but cannot be ruled out with other leaving groups. 46 …”

“…It has been reported that these mechanisms prevail when arenediazonium salts are used as electrophilic reagents in Cu(I)-assisted nucleophilic substitution, but cannot be ruled out with other leaving groups. 46 To test the versatility of the methodology, Pd@CALB4 was evaluated in the C-H activation of 1 using iodobenzene (4) at 60ºC in methanol without additional base (Figure 5). A conversion of 52% was obtained after 24 h incubation, with a TOF value of 0.75 h -1.…”

Ullmann homocoupling of arenediazonium salts in a deep eutectic solvent. Synthetic and mechanistic aspects

“…On these basis, we decided, in the light our previous researches, 13 to use DES as privileged solvent. Obviously, we have to choose a DES without halide salts as hydrogen bond acceptor to avoid Sandmeyer reactions.…”

Design of a New Chiral Deep Eutectic Solvent Based on 3-Amino-1,2-propanediol and Its Application in Organolithium Chemistry

“…We decide to explore the reactivity of benzyl chloride 4 with n -BuLi in different DESs ( Table 2 ), including the eutectic mixture Gly:KF 6:1 ( Table 2 , entry 4), recently designed and exploited by some of us [ 44 , 45 , 46 ].…”