Schmittel M, Peters K, Peters E M, Haeuseler A, Trenkle H
FB 8 - OC1 (Chemie-Biologie) der Universität-GH Siegen, Adolf-Reichwein-Strasse, D-57068 Siegen, Germany.
J Org Chem. 2001 May 18;66(10):3265-76. doi: 10.1021/jo0057093.
A wide range of enol carbonate, carbamate, and ester radical cations is characterized in solution by cyclic voltammetry and EPR spectroscopy. Preparative transformations using one-electron oxidants or anodic oxidation yield benzofurans after O-CO bond cleavage. Mechanistic investigations and direct detection of radical intermediates reveal that all enol radical cations undergo exclusively O-CO bond cleavage to provide alpha-carbonyl cations and acyl (or alternatively, alkoxyacyl and aminoacyl) radicals, respectively. The kinetics of the mesolytic fragmentation and the influence of nucleophilic additives have been determined using fast-scan cyclic voltammetry.
通过循环伏安法和电子顺磁共振光谱对多种烯醇碳酸酯、氨基甲酸酯和酯自由基阳离子在溶液中的特性进行了表征。使用单电子氧化剂或阳极氧化进行的制备性转化在O-CO键断裂后生成苯并呋喃。机理研究和自由基中间体的直接检测表明，所有烯醇自由基阳离子都仅发生O-CO键断裂，分别生成α-羰基阳离子和酰基（或者烷氧基酰基和氨基酰基）自由基。使用快速扫描循环伏安法测定了均裂裂解的动力学以及亲核添加剂的影响。
