Mori Akinori, Mizusaki Tomoteru, Ikawa Takashi, Maegawa Tomohiro, Monguchi Yasunari, Sajiki Hironao
Laboratory of Medicinal Chemistry, Gifu Pharmaceutical University, Mitahora-higashi 5-6-1, Gifu 502 8585, Japan.
Chemistry. 2007;13(5):1432-41. doi: 10.1002/chem.200601184.
A method for the deoxygenation of phenolic hydroxy groups via aryl triflates or mesylates has been established by using a combination of Pd/C-Mg-MeOH. The addition of NH(4)OAc to the system markedly accelerated the reaction rate and expanded the scope of the reaction. Mechanistic studies suggested that a single-electron transfer process from the Pd(0) center to the benzene ring is involved in the reduction of aryl sulfonates and that NH(4)OAc works as a solubilization reagent of the Mg salt and as an accelerator of the electron transfer, thus enhancing the reaction process. Our method was also applicable to the regioselective deuteration of benzene derivatives with CH(3)OD as the solvent and deuterium source: the original hydroxy group could be efficiently replaced with a deuterium atom.
通过使用钯碳-镁-甲醇的组合，已经建立了一种经由芳基三氟甲磺酸酯或甲磺酸酯对酚羟基进行脱氧的方法。向该体系中加入醋酸铵显著加快了反应速率并扩大了反应范围。机理研究表明，从钯（0）中心到苯环的单电子转移过程参与了芳基磺酸盐的还原，并且醋酸铵起到镁盐的增溶剂和电子转移促进剂的作用，从而增强了反应过程。我们的方法也适用于以氘代甲醇为溶剂和氘源对苯衍生物进行区域选择性氘代：原来的羟基可以被一个氘原子有效取代。
