C-H and C-F Bond Activation Reactions of Fluorinated Propenes at Rhodium: Distinctive Reactivity of the Refrigerant HFO-1234yf

被引：27
作者：
Talavera, Maria [1 ]
von Hahmann, Cortney N. [1 ]
Mueller, Robert [2 ]
Ahrens, Mike [1 ]
Kaupp, Martin [2 ]
Braun, Thomas [1 ]
机构：
[1] Humboldt Univ, Dept Chem, Brook Taylor Str 2, D-12489 Berlin, Germany
[2] Tech Univ Berlin, Inst Chem, Sekr C7, Theoret Chem Quantenchem, Str 17 Juni 135, D-10623 Berlin, Germany
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 31期
关键词：
C-H activation; fluorine; olefins; rhodium; silanes; CATALYTIC HYDRODEFLUORINATION; STEREOSELECTIVE-SYNTHESIS; GEM-DIFLUOROALKENES; USEFUL TOOL; COMPLEXES; FUNCTIONALIZATION; PALLADIUM; ACIDS; TETRAFLUOROETHYLENE; HEXAFLUOROPROPENE;
D O I：
10.1002/anie.201902872
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The reaction of [Rh(H)(PEt3)(3)] (1) with the refrigerant HFO-1234yf (2,3,3,3-tetrafluoropropene) affords an efficient route to obtain [Rh(F)(PEt3)(3)] (3) by C-F bond activation. Catalytic hydrodefluorinations were achieved in the presence of the silane HSiPh3. In the presence of a fluorosilane, 3 provides a C-H bond activation followed by a 1,2-fluorine shift to produce [Rh{(E)-C(CF3)=CHF}(PEt3)(3)] (4). Similar rearrangements of HFO-1234yf were observed at [Rh(E)(PEt3)(3)] [E=Bpin (6), C7D7 (8), Me (9)]. The ability to favor C-H bond activation using 3 and fluorosilane is also demonstrated with 3,3,3-trifluoropropene. Studies are supported by DFT calculations.
引用
收藏
页码：10688 / 10692
页数：5
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