Catalytic CF Bond Activation of Hexafluoropropene by Rhodium: Formation of (3,3,3‐Trifluoropropyl)silanes

Abstract

A clean break: The novel catalytic conversion of hexafluoropropene into (3,3,3‐trifluoropropyl)silanes by CF activation has been developed (see scheme). The reactions are catalyzed by the rhodium complex [Rh{(Z)‐CFCF(CF3)}(PEt3)3], proceed at room temperature, and are highly selective.

Conversion of Carbon–Fluorine Bonds α to Transition Metal Centers to Carbon–Hydrogen, Carbon–Carbon, and Carbon–Heteroatom Bonds

“…[8,51,[112][113] Likewise, some fluorinated alkenes have yielded to C-F bond activation. [43,48,58] In contrast to aromatic or other unsaturated fluorocarbons containing π electrons, saturated PFCs have no strong binding site for interaction with a metal center. Radical pathways for the activation of these bonds by Zr and Hf hydrides have been successful, [114][115] as well as the recently reported conversion of aliphatic C-F bonds to C-H bonds using the R 3 Si + cation as a catalyst and R 3 SiH as the source of hydrogen atoms.…”

“…With both positive and negative properties in mind, our group and others [43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58] have approached the selective activation of C-F bonds using transition metal complexes. A different positive role for compounds containing C-F bonds has now evolved in bioorganic chemistry, [24][25][26] leading to significant recent interest in generating new methodology for synthesis of carbon stereocenters bearing a fluorine or fluoroalkyl group.…”

Catalytic Transformations of Fluorinated Olefins

“…In the presence of triphenylsilane and a catalytic amount of ((Z)-perfluoropropenyl)Rh(PEt 3 ) 3 , hexafluoropropylene is selectively transferred into 3,3,3-trifluoropropylsilane (Scheme 13) [37]. This catalytic reaction is very selective and only 3,3,3-trifluoropropylsilane is generated (TON ¼ 90).…”

Fluorine as a ligand substituent in organometallic chemistry: A second chance and a second research career

“…Much of this recent activity is driven by the need for synthetic procedures to incorporate fluorine or a CF 3 group strategically in the synthesis of pharmaceuticals or PET reagents, leading to the development of new methodology for formation of C-F and C-CF 3 bonds [110][111][112][113][114][115][116][117][118][119][120][121][122]. Organometallic chemistry involving the chemical functionalization of C-F bonds also continues to be an active field [123][124][125][126][127][128][129][130][131][132][133][134][135][136].…”