Grignard reagent formation via C–F bond activation: a centenary perspective

Abstract

Examples of Grignard reagents obtained by C-F bond activation with magnesium kept appearing in the literature over the last century. Due to the high bond dissociation energy of the C-F...

Heterolytic versus Homolytic: Theoretical Insight into the Ni0-Catalyzed Ph–F Bond Activation

“…Transition-metal-catalyzed aryl fluoride (ArF) functionalizations have reached an impressive level of sophistication and efficiency during the past two decades because these routes not only provide alternative methods for synthesis of structurally diverse molecules from organic fluoride compounds but also offer new opportunities to exploit the prevalent commercial sources of ArF. − Although other aryl halides (ArX; X = Cl, Br, I) and aryl triflates have been used as electrophiles in many cross-coupling reactions, ArF is much more challenging and thus less developed. − Generally, ArF is unreactive due to both kinetic and thermodynamic reasons because the Ar–F bond is more electronically inert and the bond dissociation energy (BDE) of the Ar–F bond is exceptionally larger than those of Ar–X bonds . In this context, the concerted oxidative addition of the Ar–F bond to low covalent transition-metal complexes rarely succeeds. − However, the successful development of hydrogenation and amination, , and formation of several C–C bonds − of ArF have been reported recently.…”

Recent advances in C–F bond activation of trifluoromethylated carbonyl compounds and derivatives

“…2 Alternatively, C–F bond functionalization from readily available polyfluorinated compounds represents an attractive and promising approach, which serves as an important complementary route to partially fluorinated compounds. 3 Although several reviews on the C–F functionalization of CF 3 -containing compounds have recently been published by our group and other researchers, 3 g , j – p they only focus on one or a few aspects of the topic. In view of this rapidly developing field, there is a great need for a critical review of the C–F bond activation of specific compounds.…”

Ni-catalyzed C–F activation to construct C–P bond with P–P(O) and P(O)OR mediation

“…Compounds containing the C–F bond, which are available from commercial sources, 1,2 can be utilized as platform chemicals for the feasible synthesis of value-added products, including organophosphorus, organoboron, organosilicon, amines, etc . 3–8 Their synthetic processes rely on C–F bond activation and functionalization. However, the intrinsic high bond-dissociation energy of the C–F bond limits the application of the aforementioned synthesis methods.…”