A new pathway was developed for the synthesis of benzyl benzoates via TBAI-mediated oxidative self-coupling of benzyl bromides in the presence of tert-butyl hydroperoxide (TBHP) as an oxidant under solvent-free conditions. Various derivatives of precursors including electron donating and withdrawing groups as well as heteroaromatic and polycyclic benzyl bromides were subjected to the reaction conditions and converted to the corresponding benzylic esters in good to high yields. Mechanistic studies showed that this reaction did not take place via the radical pathway and tert-butyl peresters and benzoic acids are two key intermediates in this transformation.

中文翻译：

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无溶剂条件下TBAI催化的苄基溴的氧化自偶联：合成苯甲酸苄酯的新途径

在无溶剂条件下，在叔丁基氢过氧化物（TBHP）作为氧化剂存在下，通过TBAI介导的苄基溴的氧化自偶联，开发了一种新的途径，用于合成苯甲酸苄酯。使包括给电子和吸电子基团的前体的各种衍生物，以及杂芳族和多环苄基溴化物经受反应条件，并以良好或高收率转化成相应的苄基酯。机理研究表明，该反应不是通过自由基途径发生的，叔丁基过酸酯和苯甲酸是该转化过程中的两个关键中间体。