Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO(2).
Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO(2).
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DOI：
10.1021/acscatal.6b02124
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发表时间：
2016-10-07
期刊：
影响因子：
12.9
通讯作者：
Martin, Ruben
中科院分区：
文献类型：
--
作者：
Borjesson, Marino;Moragas, Toni;Gallego, Daniel;Martin, Ruben
近年来，以 CO2 作为 C1 源的金属催化有机（拟）卤化物还原羧化的发展，代表了用于制备羧酸的现有方法的潜在强大替代方案，以及众多药物和显示出重要生物学特性的分子中的特权基序。虽然最初被视为奇异的交叉偶联反应，但仔细研究文献数据表明，这些过程已成为沃土，允许利用各种偶联伙伴，即使是特别具有挑战性的底物组合。至于其他相关的交叉亲电子试剂场景，绝大多数有机（拟）卤化物的还原羧化反应具有简单、条件温和和广泛的官能团兼容性的特点，表明这些过程可以在后期多样化中实现。这一观点描述了有机（拟）卤化物的金属催化还原羧化从大阪田开创性的化学计量工作开始到现在的演变。特别强调这些偶联过程的反应性，底物范围从芳基、乙烯基、苄基到未活化的烷基（拟）卤化物。尽管取得了令人印象深刻的进步，但仍然缺乏详细说明这些过程的复杂机制的全面研究。最近的一些经验证据揭示了所用配体的取代模式所产生的有趣的二分法；然而，这些反应催化循环中的一些基本步骤仍然是推测性的，在许多情况下调用了典型的交叉偶联过程。尽管是暂定的，但我们预计这些过程可能会根据所使用的基质属于多个不同的机械类别，这表明旨在揭示这些过程的机械基础的研究可能会在这个充满活力的专业领域带来新的和创新的研究基础。
The recent years have witnessed the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with CO2 as C1 source, representing potential powerful alternatives to existing methodologies for preparing carboxylic acids, privileged motifs in a myriad of pharmaceuticals and molecules displaying significant biological properties. While originally visualized as exotic cross-coupling reactions, a close look into the literature data indicates that these processes have become a fertile ground, allowing for the utilization of a variety of coupling partners, even with particularly challenging substrate combinations. As for other related cross-electrophile scenarios, the vast majority of reductive carboxylation of organic (pseudo)halides are characterized by their simplicity, mild conditions, and a broad functional group compatibility, suggesting that these processes could be implemented in late-stage diversification. This perspective describes the evolution of metal-catalyzed reductive carboxylation of organic (pseudo)halides from its inception in the pioneering stoichiometric work of Osakada to the present. Specific emphasis is devoted to the reactivity of these coupling processes, with substrates ranging from aryl-, vinyl-, benzyl- to unactivated alkyl (pseudo)halides. Despite the impressive advances realized, a comprehensive study detailing the mechanistic intricacies of these processes is still lacking. Some recent empirical evidence reveal an intriguing dichotomy exerted by the substitution pattern on the ligands utilized; still, however, some elementary steps within the catalytic cycle of these reactions remain speculative, in many instances invoking a canonical cross-coupling process. Although tentative, we anticipate that these processes might fall into more than one distinct mechanistic category depending on the substrate utilized, suggesting that investigations aimed at unraveling the mechanistic underpinnings of these processes will likely bring new and innovative research grounds in this vibrant area of expertise.
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