Preparation of perfluoro compounds through the regioselective cleavage of a carbon-fluorine bond

2016 Fiscal Year Final Research Report

• Project/Area Number: 25708018
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Partial Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: Ohashi Masato 大阪大学, 工学(系)研究科(研究院), 准教授 (60397635)
• Project Period (FY): 2013-04-01 – 2017-03-31
• Keywords: 炭素フッ素結合活性化 / 分子変換反応 / パーフルオロ化合物 / パラジウム / ニッケル / 銅

Outline of Final Research Achievements

The Pd(0)-mediated regioselective C-F bond cleavage of perfluoroalkene has been developed by adopting the proper choice of the Lewis acid additive. Thus, the addition of tris(pentafluorophenyl)borane to eta2-hexafluoro propylene Pd(0) complex allowed the sp3-C-F bond cleavage in a selective manner to yield a cationic perfluoroallyl complex. In contrast, the use of BF3-etherate resulted in the quantitative sp2-C-F bond cleavage to yield a perfluoropropenyl complex.
We found that the allylic C-F bond cleavage would be the kinetically dominant process in our system, and that both steric hindrance and nucleophilicity of the counter anion or the resultant conjugated base would be the key to determine the structure of C－F bond cleavage product.

Free Research Field

有機金属化学、錯体化学、触媒化学