Lorwongkamol Phurinat, Watanabe Taito, Kitada Masaki, Uetake Yuta, Saga Yutaka, Kambe Tetsuya, Kondo Mio, Masaoka Shigeyuki
Division of Applied Chemistry, Graduate School of Engineering, The University of Osaka, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Department of Chemistry, School of Science, Institute of Science Tokyo, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8551, Japan.
JACS Au. 2025 Aug 25;5(9):4170-4177. doi: 10.1021/jacsau.5c00665. eCollection 2025 Sep 22.
The molecular photocatalyst -Re-(2,2'-bipyridine)-(CO)Cl () is well established and has been extensively investigated for the highly active and selective conversion of CO to CO. However, its reactivity in processes other than CO reduction has rarely been explored. Herein, we report the application of as a catalyst for the visible-light-driven carboxylation of an alkene using CO, with phenyl vinyl sulfone () serving as a model substrate. The catalytic system successfully catalyzed the carboxylation of to its corresponding carboxylic acid, with complete suppression of CO formation throughout the reaction. A turnover number (TON) of up to 2600, along with excellent regioselectivity, was achieved under optimized conditions. Control experiments revealed the key role of each reaction component, while isotope labeling with CO confirmed that the carboxyl group originated from CO. Furthermore, mechanistic investigations suggested that the Re-CO intermediate reacts directly with the alkene. These findings highlight the potential of Re-based molecular complexes for broader reactivities and expand their applicability in sustainable synthetic transformations.
分子光催化剂Re-(2,2'-联吡啶)-(CO)Cl（）已得到充分确立，并已针对将CO高效且选择性地转化为CO进行了广泛研究。然而，其在CO还原以外的过程中的反应活性鲜有探索。在此，我们报道了将用作催化剂，以苯乙烯基砜（）为模型底物，利用CO实现可见光驱动的烯烃羧基化反应。该催化体系成功催化转化为其相应的羧酸，且在整个反应过程中完全抑制了CO的生成。在优化条件下，实现了高达2600的转化数（TON）以及出色的区域选择性。对照实验揭示了各反应组分的关键作用，而用CO进行同位素标记证实羧基源自CO。此外，机理研究表明Re-CO中间体直接与烯烃反应。这些发现凸显了基于Re的分子配合物具有更广泛反应活性的潜力，并拓展了它们在可持续合成转化中的适用性。
