Shen Hua-Chen, Li Jian-Jun, Wang Peng, Yu Jin-Quan
State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences CAS 345 Lingling Road Shanghai 200032 P. R. China
School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences 1 Sub-lane Xiangshan Hangzhou 310024 P. R. China.
Chem Sci. 2024 Sep 4;15(38):15819-24. doi: 10.1039/d4sc03802a.
The transition metal-catalyzed -C-H functionalization of alcohols and their hydroxylamine derivatives remains underdeveloped. Herein, we report an efficient -C-H arylation of both phenylethyl and benzylic alcohols and their hydroxylamine derivatives using a readily removable oxime ether directing group. Using electronically activated 2-carbomethoxynorbornene as the transient mediator and 3-trifluoromethyl-2-pyridone as the enabling ligand, this reaction features a broad substrate scope and good functional group tolerance. More importantly, with this oxime-directed -C-H functionalization, this method provides a dual approach for efficient access to both -substituted alcohols and hydroxylamines using two sets of simple deprotection conditions. This protocol leads to the efficient synthesis of bioactive compounds possessing promising reactivities for the treatment of pulmonary fibrosis.
过渡金属催化的醇及其羟胺衍生物的-C-H官能化反应仍未得到充分发展。在此，我们报道了一种使用易于去除的肟醚导向基团，对苯乙醇和苄醇及其羟胺衍生物进行高效的-C-H芳基化反应。以电子活化的2-甲氧羰基降冰片烯作为瞬态介质，3-三氟甲基-2-吡啶酮作为促进配体，该反应具有广泛的底物范围和良好的官能团耐受性。更重要的是，通过这种肟导向的-C-H官能化反应，该方法提供了一种双重方法，可使用两组简单的脱保护条件高效地获得α-取代的醇和羟胺。该方案可高效合成对治疗肺纤维化具有潜在活性的生物活性化合物。
