Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
J Am Chem Soc. 2011 Aug 10;133(31):11840-3. doi: 10.1021/ja202880n. Epub 2011 Jul 18.
Generation of carbocations by the "cation 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 carbocations. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemical-chemical oxidation can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substituted alkenes to 1,2-diketones. Moreover, the oxidation of unsaturated compounds bearing a nucleophilic group in an appropriate position gives cyclized carbonyl compounds.
通过“阳离子池”方法生成碳正离子，然后与二甲亚砜（DMSO）反应，得到相应的烷氧基锍离子。烷氧基锍离子也可以通过电化学生成的碳正离子与原位 DMSO 捕获来生成。所得的烷氧基锍离子通过用三乙胺处理转化为羰基化合物。本集成电化学-化学氧化可用于二芳基甲烷氧化为二芳基酮、甲苯氧化为苯甲醛、以及芳基取代的烯烃氧化为 1,2-二酮。此外，在适当位置具有亲核基团的不饱和化合物的氧化可得到环状羰基化合物。
