Das Suman, Reilly Maeve A, Dorn Stanna K, Pearson Allison M, Brown M Kevin
Department of Chemistry, Indiana University, 800 E. Kirkwood Ave, Bloomington, 47401, Indiana.
Angew Chem Int Ed Engl. 2025 May 26;64(22):e202424073. doi: 10.1002/anie.202424073. Epub 2025 Mar 27.
Palladium-catalyzed cross coupling of enolates-α-arylation-is an established method for chemical synthesis. A major challenge in the field is control of stereochemistry for the α-carbon. This is typically due to facile epimerization under the basic reaction conditions for α-arylation. In this study, an alternative approach is presented that involves the Pd/Cu-catalyzed arylboration of electron deficient alkenes. The products are generated with high levels of diastereoselectivity for a broad range of substitution patterns. Enantioselective variants are also presented in addition to product derivatizations.
钯催化的烯醇盐α-芳基化交叉偶联是一种成熟的化学合成方法。该领域的一个主要挑战是对α-碳立体化学的控制。这通常是由于在α-芳基化的碱性反应条件下容易发生差向异构化。在本研究中，提出了一种替代方法，该方法涉及钯/铜催化的缺电子烯烃的芳基硼化反应。对于广泛的取代模式，产物以高非对映选择性生成。除了产物衍生化之外，还介绍了对映选择性变体。
