The Kolbe or Non‐Kolbe electrolysis is one of the most studied electro‐organic reactions and a fundamental pillar of organic chemistry. In contrast to classical Kolbe dimerization of monocarboxylic acids, dicarboxylic acids are only scarcely subject for Kolbe electrolysis in the literature despite their vast natural abundance. Herein, we report on the intramolecular biradical recombination of dicarboxylic acids as a green way to prepare alkenes or alkynes over a newly proposed mechanistic route. Proceeding over a radical mechanism without dimerization, it clearly stands out from classical (Non‐)Kolbe electrolysis. In the presence of non‐toxic aqueous solvents, the desired products form in excellent yields (up to 83 %), which are the highest reported for this substrate class. Once feasibility had been shown for the electrolysis of methylsuccinic acid, we could demonstrate its application to a broad scope of different dicarboxylic acids.

中文翻译：

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二羧酸分子内双自由基重组为不饱和化合物：旧的科尔贝反应的新方法

Kolbe或Non-Kolbe电解是研究最多的有机电反应之一，是有机化学的基本支柱。与传统的一元羧酸的Kolbe二聚化相反，尽管二元羧酸具有丰富的自然丰度，但在文献中几乎不涉及Kolbe电解。在此，我们报道了二羧酸的分子内双自由基重组，这是通过新提出的机理路线制备烯烃或炔烃的绿色方法。在不进行二聚化的自由基机理上，它显然与经典的（非）Kolbe电解法脱颖而出。在无毒的水性溶剂存在下，所需的产物以优异的产率（高达83％）形成，这是此类底物的最高报道。