Stefanoni Kevin Klaus, Schmitz Matthias, Treuheit Johanna, Kerzig Christoph, Wilhelm René
Institute of Organic Chemistry, Clausthal University of Technology, Leibnizstr. 6, 38678 Clausthal-Zellerfeld, Germany.
Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
J Org Chem. 2025 May 16;90(19):6491-6503. doi: 10.1021/acs.joc.5c00319. Epub 2025 May 5.
Indolizines are a promising class of biologically active compounds. However, photocatalytic methods for their selective derivatization are scarce in the literature. Herein, a mild, simple, and chemoselective protocol for the synthesis of 3-(trifluoromethyl)indolizine has been developed. The desired products were obtained in good to excellent yields and can be easily obtained on a gram scale. By tuning the redox properties of a Ru-based photocatalyst, it is possible to achieve competitive yields and further apply the optimized conditions to a broad variety of substrates. This method tolerates many functional groups and, therefore, can be used for late-stage functionalization. Our combined theoretical and spectroscopic findings revealed that the superior dyad-like ruthenium catalyst developed in this study has a completely different electronic nature of both key species that are crucial for efficient photoredox catalysis compared to commonly used homoleptic ruthenium complexes.
中氮茚是一类具有前景的生物活性化合物。然而，文献中关于其选择性衍生化的光催化方法却很少。在此，已开发出一种温和、简单且具有化学选择性的合成3-(三氟甲基)中氮茚的方法。所需产物以良好至优异的产率获得，并且可以很容易地以克级规模得到。通过调节钌基光催化剂的氧化还原性质，有可能实现具有竞争力的产率，并将优化后的条件进一步应用于多种底物。该方法能耐受许多官能团，因此可用于后期官能团化。我们结合理论和光谱研究结果表明，与常用的均配钌配合物相比，本研究中开发的优异的二元类钌催化剂对于高效光氧化还原催化至关重要的两个关键物种具有完全不同的电子性质。
