Light-Mediated Synthesis of Aliphatic Anhydrides by Cu-Catalyzed Carbonylation of Alkyl Halides,Journal of the American Chemical Society

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Light-Mediated Synthesis of Aliphatic Anhydrides by Cu-Catalyzed Carbonylation of Alkyl Halides
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-04-19 , DOI: 10.1021/jacs.3c01224
Pinku Tung ₁ , Neal P Mankad ₁

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Acid anhydrides are valuable in the chemical industry for their role in synthesizing polymers, pharmaceuticals, and other commodities, but their syntheses often involve multiple steps with precious metal catalysts. The simplest anhydride, acetic anhydride, is currently produced by two Rh-catalyzed carbonylation reactions on a bulk scale for its use in synthesizing products ranging from aspirin to cellulose acetate. Here, we report a light-mediated, Cu-catalyzed process for producing aliphatic, symmetric acid anhydrides directly by carbonylation of alkyl (pseudo)halides in a single step without any precious metal additives. The transformation requires only simple Cu salts and abundant bases to generate a heterogeneous Cu⁰ photocatalyst in situ, maintains high efficiency and selectivity upon scale-up, and operates by a radical mechanism with several beneficial features. This discovery will enable the engineering of bulk processes for producing commodity anhydrides efficiently and sustainably.

中文翻译：

Cu 催化烷基卤化物羰基化光催化合成脂肪族酸酐

酸酐因其在合成聚合物、药物和其他商品中的作用而在化学工业中很有价值，但它们的合成通常涉及使用贵金属催化剂的多个步骤。最简单的酸酐，乙酸酐，目前通过两个 Rh 催化的羰基化反应大规模生产，用于合成从阿司匹林到醋酸纤维素等产品。在这里，我们报告了一种光介导的 Cu 催化工艺，在不添加任何贵金属添加剂的情况下，直接通过烷基（拟）卤化物的羰基化直接生产脂肪族对称酸酐。该转化仅需要简单的铜盐和丰富的碱就可以原位生成多相 Cu ⁰光催化剂，在放大时保持高效率和选择性，并通过具有多种有益特征的激进机制运作。这一发现将使批量过程的工程设计能够高效、可持续地生产商品酸酐。

更新日期：2023-04-19

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