Catalytic Transformations of Fluorinated Olefins

Abstract

Progress in the development of catalytic transformation reactions of fluorinated olefins is reviewed. Four different types of transition-metalcatalyzed transformations have been distinguished: (a) oligomerization, (b) hydrodefluorination, (c) C-X bond formation via C-F bond cleavage, and (d) C-C bond formation via C-F bond cleavage.

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

“…24 Among reactions of aliphatic hydrofluorocarbons in solution, we draw attention to the reactions of CH 3 F and CHF 3 at iridium pincer complexes 42 and the discovery of niobium complexes that are selective for activation of benzylic CF 3 groups, even in the presence of C-H bonds. 43 Carbon-fluorine bond activation has been the subject of numerous recent reviews, [33][34][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] but competing C-H bond activation receives little attention in most of these publications. Two reviews pay particular attention to partially fluorinated substrates and C-H activation, one on nickel chemistry 62 and the other on organometallic chemistry particularly with fluorobenzene and difluorobenzene.…”

A T-shaped Ni[κ2-(CF2)4–] NHC complex: unusual Csp3–F and M–CFbond functionalization reactions

“… 11 As far as we know, this reaction is the only example of a perfluoro-metallacyclopentane participating in a catalytic cycle. 12 …”

Competing C–H and C–F bond activation reactions of a fluorinated olefin at Rh: a fluorido vinylidene complex as an intermediate in an unprecedented dehydrofluorination step

“…[1][2][3][4][5] In this regard, both C-H and C-F bond activation reactions of HFOs have been described using transition metal complexes, main group elements or heterogeneous catalysts. [6][7][8][9][10][11][12] Commonly, the C-F bond activation is promoted by the formation of stable bonds such as H-F, B-F, Si-F or Al-F bonds among others. [13][14][15][16][17][18] At rhodium, the complexes [Rh(E)(PEt 3 ) 3 ] (E ¼ H, F, boryl, silyl, germyl) exhibit distinct reaction pathways for the C-F or C-H bond activation of HFOs.…”

“… 1–5 In this regard, both C–H and C–F bond activation reactions of HFOs have been described using transition metal complexes, main group elements or heterogeneous catalysts. 6–12 Commonly, the C–F bond activation is promoted by the formation of stable bonds such as H–F, B–F, Si–F or Al–F bonds among others. 13–18 …”