Direct functionalization of aliphatic alcohols by transition metal catalysis

2014 Fiscal Year Final Research Report

• Project/Area Number: 24550122
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Osaka Prefecture University
• Principal Investigator: FUKUYAMA Takahide 大阪府立大学, 理学(系)研究科(研究院), 准教授 (60332962)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: アルコール / 直接官能基化 / ケトン / アミド / ニトリル / ルテニウムヒドリド / 水素移動反応 / 異性化

Outline of Final Research Achievements

Direct functionalization of aliphatic alcohols was investingated. α-Alkylation of carbonyl compounds, such as ketones, amides, and acetonitrile, using primary aliphatic alcohols was effectively catalyzed by RuHCl(CO)(PPh3)3. The present reaction would proceed via RuH-catalyzed transfer dehydrogenation of alcohols to aldehydes, which then undergo base promoted aldol condensation with carbonyl compounds to give α,β-unsaturated compounds. Finally transfer hydrogenation of thus formed α,β-unsaturated compounds with alcohols would provide the α-alkylated products. RuHCl(CO)(PPh3)3 was also found to be effective for selective olefin isomerization of protected homoallyl alcohols.　　The reaction of homoallyl carbonate with malonic acid esters gave coupling product via sequential olefin isomerization and allylic alkylation reaction.

Free Research Field

化学