Grignard-type Reaction through the Generation of Oraganometal Reagent from Carboxylates

2013 Fiscal Year Final Research Report

• Project/Area Number: 24655085
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Kyushu University
• Principal Investigator: KUWANO Ryoichi 九州大学, 理学(系)研究科(研究院), 教授 (20273477)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Keywords: ニッケル / 求核付加 / 酢酸アリル / アルデヒド / （π－アリル）錯体 / 電子移動 / 有機金属触媒 / 極性転換

Research Abstract

A mixture of allyl acetate and an aldehyde was heated in an aprotic solvent in the presence of 1,10-phenanthroline-nickel catalyst, zinc powder, and sodium iodide. The resulting mixture gave the desired homoallyl alcohol in good yield. In this transformation, the allyl group of the ester substrate undergoes umpolung to give a nucleophilic species. The resulting species attacks the carbonyl carbon of the aldehyde substrate. The iodide anion may facilitate the electron transfer from zinc powder to the nickel atom.