Carbon-Fluorine Bond Activation via beta-Fluorine Elimination

2015 Fiscal Year Final Research Report

• Project/Area Number: 26870079
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry; Organic chemistry
• Research Institution: University of Tsukuba
• Principal Investigator: FUJITA Takeshi 筑波大学, 数理物質系, 助教 (60603066)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Keywords: 有機合成化学 / フッ素 / 遷移金属触媒 / 炭素-フッ素結合活性化 / フルオロアルケン / 脱離

Outline of Final Research Achievements

I achieved vinylic and allylic C-F bond activation based on beta- and alpha-fluorine elimination from nickelacycle intermediates.
I have developed two types of defluorinative coupling reactions of 2-trifluoromethyl-1-alkenes and alkynes via beta-fluorine elimination from nickelacycles. Addition of Et3SiH enabled a catalytic synthesis of 1,1-difluoro-1,4-dienes, while diboron compounds afforded 2-fluorocyclopentadienes via cleavage of two C-F bonds in a trifluoromethyl group. In both reactions, beta-fluorine elimination from the intermediary nickeracyclopentenes served as a key elementary step. I have also achieved nickel-catalyzed [2+2+2] cyclization of 1,1-difluoroethylene and alkynes via sequential alpha-fluorine and beta-hydrogen elimination, which provides a direct method for the synthesis of fluoroarenes. An alkylborate reagent effectively promoted its catalytic reaction.

Free Research Field

有機合成化学