alpha-Arylation of Heteroatom-Containing Aliphatic Compounds through Homolytic Aromatic Substitution

2018 Fiscal Year Final Research Report

• Project/Area Number: 16H04151
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kwansei Gakuin University
• Principal Investigator: Shirakawa Eiji 関西学院大学, 理工学部, 教授 (70273472)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Keywords: ラジカル反応 / 炭素-炭素結合形成反応 / 芳香族ラジカル置換反応

Outline of Final Research Achievements

A new method of direct alpha-arylation of heteroatom-containing aliphatic compounds (R-H: alkylamines, alkylamides, ethers, alcohols,...) using aromatic compounds having a heteroatom leaving group (Ar-X) and a radical source (Z-Z) giving R-Ar has been developed. In most cases, a radical chain consisting of homolytic aromatic substitution on Ar-X by R radical, generated through hydrogen abstraction by Z radical, and regeneration of R radical through hydrogen abstraction from R-H by the resulting X radical is operative, and thus just a small amount of Z-Z is required.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

遷移金属を用いずにC-H結合を直接活性化して炭素-炭素結合形成に結び付ける新しい手法の開発という点で学術的意義がある．また，ここでは基質以外のものとしては，基本的には少量のラジカル源・中和のための塩基・溶媒しか必要としないため，グリーンケミストリーに理念に則っており，持続可能な社会の実現という観点からも意義がある．