32134-69-3Relevant articles and documents
Gold-catalyzed oxidative acyloxylation of arenes
Pradal, Alexandre,Toullec, Patrick Y.,Michelet, Veronique
supporting information; experimental part, p. 6086 - 6089 (2011/12/22)
A variety of nonactivated hindered aromatic rings are acyloxylated (22 examples, up to 83% yield) in the presence of PPh3AuCl as the catalyst and di(acetoxy)iodobenzene as the oxidant. The reaction proceeds at 110 °C in an acid media and allows the formation of both hindered acetoxy and acyloxy derivatives. This methodology nicely complements the Pd-catalyzed arene acyloxylation reaction, which is not operating on hindered substrates and allows the Au-catalyzed unprecedented acyloxylation reaction of arenes, implying various carboxylic acids.
Aromatic Iodination: Evidence of Reaction Intermediate and of the ?-Complex Character of the Transition State
Galli, Carlo
, p. 3238 - 3245 (2007/10/02)
The reactivity of the four different procedures of aromatic iodination is compared under the same experimental conditions, and their selectivity toward two substrates in competition, i. e., mesitylene (1,3,5-trimethylbenzene, MES) and durene (1,2,4,5-tetramethylbenzene, DUR), is evaluated.Two of these procedures, namely, S2O82-/I2 and Ce(IV)/I2, present strong oxidizing capacity.Since the same MES/DUR relative reactivity is obtained from the four procedures, it becomes possible to state that a common reactive intermediate, most likely the I+ ion, is generated.The use of the MES/DUR mechanistic probe allows one to describe the reactivity picture of the iodination reaction as one of electrophilic substitution at the aromatic nucleous, with a transition state properly represented in terms of a ?-complex.The radical cation of durene also forms when the iodination is carried out by means of oxidizing agents, but it is solely responsible for the formation of side-chain substitution products and is not involved in the nuclear substitution process.
Studies on Electrolytic Substitution Reactions. XVII. Selective Nuclear Acetoxylation of Alkylaromatic Compounds
Eberson, Lennart,Oberrauch, Ermanno
, p. 193 - 196 (2007/10/02)
Anodic nuclear monoacetoxylation of alkylaromatics (p-xylene, isodurene, mesitylene, durene) can be achieved with high selectivity with respect to the side-chain acetate by carrying out the electrolysis in the presence of Pd on carbon in a nondevided cell.This arrangement utilizes cathodically generated hydrogen to effect cleavage of the benzylic acetate as it is formed, thus continuously regenerating the substrate.The nuclear acetate which is resistant toward hydrogenolysis accumulates in the reaction moxture.
