Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Electrochemically Mediated Oxidative Transformations of Substituted 4-Methoxystilbenes: Effect of Ortho-Substituted Nucleophilic Groups

Electrochemically Mediated Oxidative Transformations of Substituted 4-Methoxystilbenes: Effect of Ortho-Substituted Nucleophilic Groups
Fong-Jiao Hong, Noel F. Thomas, Kam-Weng Chong, Yun-Yee Low, Toh-Seok Kam
A systematic study was undertaken to determine the influence of ortho′-substituted nucleophilic groups (OH, NH2, or NHR) on the reactivity of anodically generated 4-methoxy- and 3,4-dimethoxystilbene cation radicals. The results showed that when ortho-substituted nucleophilic groups such as OH and NHR are present in the other ring, both direct and crossover intramolecular cation–nucleophile reactions occur to give bisbenzofurans/bisindoles or fused bisbenzopyrans/bisquinolines, respectively. Where an additional 3-methoxy substituent is present, bridged oxocine/azocine products are formed in addition to the bisbenzopyrans/bisquinolines and bisbenzofurans/bisindoles. Mechanistic rationalization of the observed behavior is presented based on a generalized pathway involving fast cation radical dimerization following electron transfer, followed by direct and crossover trapping of the benzylic cations by the ortho-substituted oxygen and nitrogen nucleophilic groups. In the instances where an additional 3-methoxy group is present, the bridged oxocine/azocine products are also formed as a result of competing aromatic substitution (Friedel–Crafts reaction). The results have shed further light and provided additional clarification on the reactivity of anodically generated stilbene cation radicals.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00753

DOI: 10.1021/acs.joc.7b00753

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