School of Chemical Sciences, National Institute of Science Education and Research (NISER), Bhubaneswar, HBNI, Bhubaneswar 752050, Odisha, India.
J Org Chem. 2021 Oct 1;86(19):13744-13753. doi: 10.1021/acs.joc.1c01861. Epub 2021 Sep 21.
A novel methodology for the synthesis of 1,5-diketones through a one-pot isomerization-methylenation of a variety of allylic alcohols has been established for the first time. This methodology utilizes commercially available palladium acetate and easily accessible BINOL phosphoric acid. Both isomerization of allylic alcohol and oxidation of methanol occurred through a single catalyst. The practical utility of the methodology has been shown by synthesizing substituted pyridines sequential addition. Mechanistic investigation reveals the isomerization of allylic alcohols to the corresponding ketone, which ultimately undergoes methylenation, leading to 1,5-diketones, having H and HO as the only byproduct.
首次建立了一种通过各种烯丙醇的一锅异构化-甲叉化反应合成 1,5-二酮的新方法。该方法利用商业可得的醋酸钯和易得的联萘酚磷酸。烯丙醇的异构化和甲醇的氧化都通过单个催化剂进行。通过连续添加的方法合成取代吡啶，证明了该方法的实际应用。机理研究表明，烯丙醇异构化为相应的酮，最终发生甲叉化，生成 1,5-二酮，H 和 HO 是唯一的副产物。
