Hashikawa Yoshifumi, Okamoto Shu, Murata Yasujiro
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.
Chemistry. 2021 Mar 12;27(15):4864-4868. doi: 10.1002/chem.202004035. Epub 2021 Jan 7.
By nucleophilic addition of phosphite P(OMe) to a cage-opened C derivative, α-hydrophosphate and enol phosphate were obtained as kinetic and thermodynamic products, respectively. Different from classical Abramov products bearing a phosphorus-carbon bond, these products have a phosphorus-oxygen bond. The observed anomaly originates from the fully conjugated π system, which significantly stabilizes zwitterionic intermediates bearing a phosphorus-oxygen bond. The thus formed enol phosphate was found to exhibit an intense absorption band that extended to 730 nm, reflecting the intramolecular charge-transfer transitions. We also report domino phosphorylation reactions, which gave a cage-opened C derivative bearing a direct P-C bond.
通过将亚磷酸酯P(OMe)亲核加成到开笼的C衍生物上，分别得到了α-氢磷酸酯和烯醇磷酸酯作为动力学和热力学产物。与具有磷-碳键的经典阿布拉莫夫产物不同，这些产物具有磷-氧键。观察到的异常现象源于完全共轭的π体系，该体系显著稳定了带有磷-氧键的两性离子中间体。发现由此形成的烯醇磷酸酯表现出延伸至730 nm的强吸收带，这反映了分子内电荷转移跃迁。我们还报道了多米诺磷酸化反应，该反应得到了带有直接P-C键的开笼C衍生物。
