One-step Formation of Phenylacetic Acids from Benzyl Alcoholes and Carbon Dioxide with One-carbon Elongation by Electrochemical Reduction

2015 Fiscal Year Final Research Report

• Project/Area Number: 25410104
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: SENBOKU HISANORI 北海道大学, 工学(系)研究科(研究院), 准教授 (50241360)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Keywords: 二酸化炭素の固定化 / 有機電解合成 / カルボン酸 / ベンジルアルコール / フェニル酢酸 / 炭素炭素結合形成 / マグネシウム陽極 / 一段階合成

Outline of Final Research Achievements

Electrochemical direct carboxylation of benzyl alcohols having an electron-withdrawing group on the phenyl ring at the ortho or para position was achieved by constant current electrolysis using an undivided cell equipped with a platinum plate cathode and a magnesium rod anode in DMF in the presence of carbon dioxide. Reductive cleavage of the C-F bond followed by fixation of carbon dioxide efficiently took place at the benzylic position without any additive in primary and secondary benzyl alcohols to give the corresponding phenylacetic acids and 2-phenylpropanoic acids in good yields in one step. Moreover, electroreductive fixation of two molecules of carbon dioxide in each benzylic moiety of dibenzyl carbonates having an electron-withdrawing group at the para position on the phenyl ring was also accomplished by combination of the present new findings with the previous results of electrochemical carboxyltion of benzyl carbonates to give twofold phenylacetic acids in high yields.

Free Research Field

有機合成化学