Westfälische Wilhelms-Universität Münster, Chemical Biology of Ion Channels (Chembion), GRK 2515, Corrensstraße 48, D-48149 Münster, Germany.
Westfälische Wilhelms-Universität Münster, Institut für Pharmazeutische und Medizinische Chemie, Corrensstraße 48, D-48149 Münster, Germany.
Molecules. 2022 Aug 22;27(16):5342. doi: 10.3390/molecules27165342.
Natural product ()-anethole was isomerized to ()-anethole in a photocatalytic reaction. For this purpose, a self-designed cheap photoreactor was constructed. Among 11 photosensitizers (organo and metal complex compounds), Ir(p-Bu-ppy) led to the highest conversion. Triplet energies of ()- and ()-anethole were predicted theoretically by DFT calculations to support the selection of appropriate photosensitizers. A catalyst loading of 0.1 mol% gave up to 90% conversion in gram scale. Further additives were not required and mild irradiation with light of 400 nm overnight was sufficient. As a proof of concept, ()- and ()-anethole were dihydroxylated diastereoselectively to obtain diastereomerically pure - and -configured diols, respectively.
天然产物 (-) 茴香脑在光催化反应中异构化为 (-) 茴香脑。为此，我们自行设计了一种廉价的光反应器。在 11 种光敏剂（有机和金属配合物）中，Ir(p-Bu-ppy) 导致了最高的转化率。通过 DFT 计算预测了 (-) 和 (-) 茴香脑的三重态能量，以支持选择合适的光敏剂。在克级规模下，催化剂负载量为 0.1mol%时，转化率最高可达 90%。不需要进一步添加添加剂，用 400nm 的光进行温和照射过夜就足够了。作为概念验证，(-) 和 (-) 茴香脑被立体选择性地二羟基化，分别得到非对映异构体纯的 - 和 - 构型二醇。
