93652-27-8Relevant academic research and scientific papers
DDQ catalyzed benzylic acetoxylation of arylalkanes: a case of exquisitely controlled oxidation under sonochemical activation
Kumar, Vinod,Sharma, Abhishek,Sharma, Meenakshi,Sharma, Upendra K.,Sinha, Arun K.
, p. 9718 - 9723 (2007)
Acetoxylated arylalkanes are selectively obtained via sonochemical activation of DDQ catalyzed benzylic oxidation of arylalkanes in the presence of anhydrous acetic acid. The method gives an exquisite control of benzylic acetoxylation under ultrasound, in contrast to the uncontrolled oxidation observed under conventional heating or microwave activation. In addition, the developed method could be?a useful strategy for the synthesis of industrially important enantiopure benzyl alcohols due to the easy amenability of obtained acetoxylated products toward chiral resolution.
Substituent Effect Studies of Aryl-Assisted Solvolyses. II. The Acetolysis of 2-Phenyl-2-(substituted phenyl)ethyl p-Toluenesulfonates
Fujio, Mizue,Maeda, Yasuyuki,Goto, Mutsuo,Saeki, Yoshihiro,Mishima, Masaaki,Tsuno, Yuho
, p. 3021 - 3029 (2007/10/02)
The substituent effect on the acetolysis of 2-phenyl-2-(substituted phenyl)ethyl p-toluenesulfonates had a nonlinear LArSR correlation and was explicable in terms of a competitive aryl-assisted mechanism involving the X-substituted phenyl-assisted (kXM) pathway and the unsubstituted phenyl-assisted (kXN) pathway. By the application of the iterative nonlinear least-squares method based on the LArSR Eq., the substituent effect on the overall kt was dissected into the best-fit kM correlation of ρM=-3.53 with rM=0.60, and the kN correlation of ρN=-0.88 with ?0. The ρM and rM values for the effects of assisting aryl substituents are quite close to those of the 2-methyl-2-phenylpropyl system and the small ρN value with unexalted ?0 constant for the unassisting aryls is compatible to the remote β-aryl effect. The relative rates of competing pathways dissected based on the substituent effect analysis agreed completely with the ratio of respective aryl migration products determined by the 13C-tracer method. Exact rate-product correlation demonstrates that this system involves two discrete aryl-assisted pathways, kXM and kXN, which do not cross over.
