Reconstruction of Molecular Framework by C-C Bond Formation and Cleavage via Metalacycles

2016 Fiscal Year Final Research Report

• Project/Area Number: 26288052
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Nagasaki University
• Principal Investigator: KIMURA Masanari 長崎大学, 工学研究科, 教授 (10274622)
• Co-Investigator(Kenkyū-buntansha): 重光 保博 長崎大学, 工学研究科, 准教授 (50432969) ; 小野寺 玄 長崎大学, 工学研究科, 助教 (90433698)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Keywords: ニッケル / 銅 / 有機アルミニウム / 有機亜鉛 / アルキン / 二酸化炭素 / 共役ジエン / カーボネート

Outline of Final Research Achievements

Although cyclic carbonates are utilized in fine chemicals and as monomers for polymerization in modern industrial synthesis, most synthetic utilities of 1,3-dioxolan-2-ones face difficulties due to the decarboxylation reaction. In this study, we have developed 4-methylene-1,3-dioxolan-2-one undergoes oxidative addition of Ni(0) catalyst in the presence of Me2Al(OMe) followed by a coupling reaction with alkynes to form unsaturated beta-ketocarboxylic acids with high regio- and stereoselectivities.
As an alternative development for CO2 fixation processes, we envisaged the three-component coupling reaction of terminal alkyne, trialkylboranes, and CO2 to yield alpha-substituted acrylic acids as a single product. Cu-catalyzed CO2 insertion reactions involving a dialkylvinylborane intermediate derived from alkynyltrialkylborate by a 1,2-alkyl group migration were carried out to afford α-alkylated acrylic acids with excellent regio- and stereoselectivities.

Free Research Field

合成化学