Catalyst-controlled functionalization of carboxylic acids by electrooxidation of self-assembled carboxyl monolayers.
Catalyst-controlled functionalization of carboxylic acids by electrooxidation of self-assembled carboxyl monolayers.
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自组装羧基单层电氧化催化羧酸功能化。
DOI：
10.1038/s41467-022-28992-4
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发表时间：
2022-03-14
影响因子：
16.6
通讯作者：
Sevov CS
中科院分区：
文献类型：
--
作者：
Hintz HA;Sevov CS
虽然羧酸的电氧化活化是一种有吸引力的合成方法，但所得的转化通常限于同偶联或进一步氧化，然后进行溶剂捕获。这些反应需要在高电位下进行大量电解，这最终使得该方法与可能提供新的和互补的产物分布的金属催化剂不相容。这项工作建立了一个罕见的和合成利用不足的策略，选择性电氧化的羧酸在氧化敏感性催化剂的存在下，控制反应选择性的概念验证。我们利用在阳极形成羧酸盐基质的自吸附单层，以促进吸附的羧酸盐在更容易氧化的催化剂上的选择性氧化。因此，与常规方法相比，反应在较低的电势、较大的法拉第效率和改进的催化剂相容性下操作，这使得反应能够用催化烯烃的选择性自由基加成的廉价Fe络合物进行。这项工作利用基板自组装在电极上，以促进选择性基板电氧化在氧化敏感催化剂的存在下。这种策略适用于羧酸与烯烃的脱羧偶联。
While the electrooxidative activation of carboxylic acids is an attractive synthetic methodology, the resulting transformations are generally limited to either homocoupling or further oxidation followed by solvent capture. These reactions require extensive electrolysis at high potentials, which ultimately renders the methodology incompatible with metal catalysts that could possibly provide new and complementary product distributions. This work establishes a proof-of-concept for a rare and synthetically-underutilized strategy for selective electrooxidation of carboxylic acids in the presence of oxidatively-sensitive catalysts that control reaction selectivity. We leverage the formation of self-adsorbed monolayers of carboxylate substrates at the anode to promote selective oxidation of the adsorbed carboxylate over a more easily-oxidized catalyst. Consequently, reactions operate at lower potentials, greater faradaic efficiencies, and improved catalyst compatibility over conventional approaches, which enables reactions to be performed with inexpensive Fe complexes that catalyze selective radical additions to olefins. This work leverages substrate self-assembly at an electrode to promote selective substrate electrooxidation in the presence of oxidatively sensitive catalysts. This strategy is applied to decarboxylative coupling of carboxylic acids with olefins.
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影响因子：
15
作者：
Lo JC;Kim D;Pan CM;Edwards JT;Yabe Y;Gui J;Qin T;Gutiérrez S;Giacoboni J;Smith MW;Holland PL;Baran PS
通讯作者：
Baran PS
影响因子：
12.9
作者：
Banerjee, Soumyodip;Han, Xu;Thoi, V. Sara
通讯作者：
Thoi, V. Sara
影响因子：
3.6
作者：
Kurihara, Hitoshi;Fuchigami, Toshio;Tajima, Toshiki
通讯作者：
Tajima, Toshiki
影响因子：
3.9
作者：
Lee, J. -Y.;Shin, S. J.;Chung, T. D.
通讯作者：
Chung, T. D.
影响因子：
64.8
作者：
Johnston CP;Smith RT;Allmendinger S;MacMillan DW
通讯作者：
MacMillan DW