4.4二氟二苯甲烷的氧化.pdf

COMMUNICATION /JACS Integrated ElectrochemicalChemical Oxidation Mediated by Alkoxysulfonium Ions Yosuke Ashikari, Toshiki Nokami, and Jun-ichi Yoshida* Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan S Supporting Information b Scheme 1. Chemical Oxidation Mediated by Alkoxysulfo- ABSTRACT: Generation of carbocations by the “cation nium Ions pool” method followed by reaction with dimethyl sulfoxide (DMSO) gave the corresponding alkoxysulfonium ions. Alkoxysulfonium ions could also be generated by in situ DMSO trapping of electrochemically generated carboca- tions. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemicalchemical oxida- tion can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substi- 0 tuted alkenes to 1,2-diketones. Moreover, the oxidation of reaction to give RR CdO is a two-electron oxidation. If substrates of lower oxidation state, for example RR0 CH , unsaturated compounds bearing a nucleophilic group in an 2 appropriate position gives cyclized carbonyl compounds. could be used to generate alkoxysulfonium ions, the overall reaction would