Ramachandran P Veeraraghavan, Alawaed Abdulkhaliq A, Hamann Henry J
Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, United States.
Org Lett. 2023 Sep 22;25(37):6902-6906. doi: 10.1021/acs.orglett.3c02643. Epub 2023 Sep 10.
A facile and selective room temperature deoxygenation of both aromatic and aliphatic carboxylic esters to ethers has been achieved by regulating the stoichiometry of the reductant, BH-NH, and the catalyst, TiCl. This first, practical borane-mediated process is compatible with various potentially sensitive functional groups and is applicable to the deoxygenative ether formation from typically challenging aromatic acid esters. Substituting BF-EtO as the catalyst alters the reaction pathway, reducing the esters to alcohols. Mechanistic insights are provided by NMR spectroscopy, deuterium labeling, and kinetic isotope studies.
通过调节还原剂BH-NH和催化剂TiCl的化学计量比，实现了芳香族和脂肪族羧酸酯在室温下简便且选择性地脱氧生成醚。这一首个实用的硼烷介导过程与各种潜在敏感官能团兼容，适用于由通常具有挑战性的芳香族酸酯进行脱氧醚化反应。用BF-EtO替代催化剂会改变反应路径，将酯还原为醇。通过核磁共振光谱、氘标记和动力学同位素研究提供了机理见解。
