Selective Cross-Ketonization of Carboxylic Acids Enabled by Metallaphotoredox Catalysis.
Selective Cross-Ketonization of Carboxylic Acids Enabled by Metallaphotoredox Catalysis.
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DOI：
10.1002/anie.202213739
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发表时间：
2022-12-23
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--
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羧酸是合成化学的有吸引力的结构单元，因为它们化学稳定、丰富并且可商购获得，具有显著的结构多样性。将两种羧酸化合成酮的过程称为酮化。这是一种潜在的有价值的转化，由于通常需要苛刻的反应条件和当偶联两种不同的羧酸时缺乏选择性，其在有机合成中未得到充分利用。本文报道了一种金属光氧化还原策略，该策略通过两种结构不同的羧酸的交叉酮化选择性地产生不对称酮。交叉选择性是通过利用不同的取代酸对关键的一个和两个电子的过程中提出的耦合机制的反应性。该方法广泛适用于各种官能化羧酸。它也可以适用于类似的空间分布的酸，通过利用它们的相对脱羧速率的差异。不对称酮可以通过两种结构不同的羧酸的选择性偶联来制备，而不需要任何一种配偶体的预活化。这种光氧化还原交叉酮化策略利用了使用两种反应物的关键单电子和双电子活化步骤的速率差异。
Carboxylic acids are attractive building blocks for synthetic chemistry because they are chemically stable, abundant, and commercially available with substantial structural diversity. The process of combining two carboxylic acids to furnish a ketone is termed ketonization. This is a potentially valuable transformation that has been underutilized in organic synthesis due to the harsh reaction conditions generally required and the lack of selectivity obtained when coupling two distinct carboxylic acids. We report herein a metallaphotoredox strategy that selectively generates unsymmetrical ketones via cross-ketonization of two structurally dissimilar carboxylic acids. Cross-selectivity is achieved by exploiting diverging reactivity of differentially substituted acids towards critical one- and two-electron processes in the proposed coupling mechanism. This method is broadly applicable to a variety of functionalized carboxylic acids. It can also be applied to acids of similar steric profile by exploiting differences in their relative rates of decarboxylation. Unsymmetrical ketones can be prepared through selective coupling of two structurally distinct carboxylic acids without the need for preactivation of either partner. This photoredox cross-ketonization strategy exploits differences in the rates of key one- and two-electron activation steps using the two reactants.
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影响因子：
15
作者：
Le CC;MacMillan DW
通讯作者：
MacMillan DW
影响因子：
5.2
作者：
Grotjahn, Sascha;Koenig, Burkhard
通讯作者：
Koenig, Burkhard
影响因子：
5
作者：
Hannah Nguyen;Wang, Yunzhu;Vlachos, Dionisios G.
通讯作者：
Vlachos, Dionisios G.
影响因子：
12.9
作者：
Kolandouzan, Kavoos;Khalaf, Ryan;Huestis, Malcolm P.
通讯作者：
Huestis, Malcolm P.
DOI：
10.1002/anie.201800701
发表时间：
2018-05-28
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Badir SO;Dumoulin A;Matsui JK;Molander GA
通讯作者：
Molander GA