Moriyama Katsuhiko, Takemura Misato, Togo Hideo
Department of Chemistry, Graduate School of Science, Chiba University , 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.
J Org Chem. 2014 Jul 3;79(13):6094-104. doi: 10.1021/jo5008064. Epub 2014 Jun 13.
A bromide-catalyzed oxidation of alcohols was developed which proceeded in the presence of an alkali metal bromide and an oxidant under mild conditions. The reaction involved an organic-molecule-free oxidation using KBr and Oxone and a Brønsted acid assisted oxidation using KBr and aqueous H2O2 solution to provide a broad range of carbonyl compounds in high yields. Moreover, the bromide-catalyzed oxidation of primary alcohols enabled the divergent synthesis of carboxylic acids and aldehydes under both reaction conditions in the presence of TEMPO. A possible catalytic mechanism was suggested on the basis of various mechanistic studies.
开发了一种溴化物催化的醇氧化反应，该反应在碱金属溴化物和氧化剂存在下于温和条件下进行。该反应包括使用KBr和过氧单磺酸钾进行无有机分子氧化，以及使用KBr和过氧化氢水溶液进行布朗斯特酸辅助氧化，以高产率提供多种羰基化合物。此外，在TEMPO存在下，伯醇的溴化物催化氧化能够在两种反应条件下分别合成羧酸和醛。基于各种机理研究提出了一种可能的催化机理。
