A catalytic CC bond‐forming reaction between aliphatic fluorohydrocarbons and arylsilanes

Abstract

C-C coupling reactions between arylsilanes and alkylfluorides are efficiently catalyzed by disilyl cation 1. Primary as well as secondary alkylfluorides were quantitatively coupled with arylsilanes; however, in the case of tertiary fluorides, the hydrodefluorination reaction predominated. Primary alkylfluorides were found to give arenes with mostly rearranged alkyl substituents. In all cases subsequent Friedel-Crafts-type chemistry occurred.

“Tamed” Silylium Ions: Versatile in Catalysis

“…[8][9][10] Multiple CÀC coupling reactions to a substrate molecule are also possible, depending on the degree of substitution on the arene ring (R'ÀH). [8][9][10] Multiple CÀC coupling reactions to a substrate molecule are also possible, depending on the degree of substitution on the arene ring (R'ÀH).…”

“…Another class of reactions catalyzed by silylium ions is the coupling of carbon atoms, with the coupling of C aryl À C aryl and C aryl À C alkyl bonds having previously been observed (Scheme 4 left). [8][9][10] Multiple CÀC coupling reactions to a substrate molecule are also possible, depending on the degree of substitution on the arene ring (R'ÀH). As with hydrodefluorination, the strong bonding tendency of the Si À F bond (D(Me 3 Si À H) = 94.6 kcal mol À1 versus D(Me 3 Si À F) = 158.0 kcal mol À1 ) is exploited to defluorinate the substrate RÀF in the first step.…”

Proton-Catalyzed, Silane-Fueled Friedel-Crafts Coupling of Fluoroarenes

“…In addition, silyl cations are instrumental in supporting aliphatic carbon-carbon bond formation (15). The mechanism is ascribed to the formation of wellknown alkyl cation equivalents, which can be trapped in classical Friedel-Crafts reactions.…”

“…V enus has the most extreme atmospheric circulation of the terrestrial planets, with the cloud-level atmosphere spinning on average 60 times faster than the planet's surface (1). This superrotation (2-10) extends to both polar regions in hemispheric spiral-like patterns of clouds (11), where it results in fast rotating, infrared-bright central vortices (12)(13)(14)(15).…”

Facile Access to Stable Silylium Ions Stabilized by N-Heterocyclic Imines

“…Moreover, Sawamura implemented a silylium ion as Lewis acid catalyst in Mukaiyama aldol and Diels-Alder reactions [16]. Catalytic C-C bond forming reactions have also been reported [17,18]. Recently, Oestreich and co-workers demonstrated that a ferrocene-based silylium ion II (Figure 1) displays catalytic activity in Diels-Alder reactions [19].…”