Perfluoroalkylation of simple inorganic molecules: A one step route to novel perfluoroalkylated compounds

Abstract

Reactions of (CH3)3SiRf (Rf = CF3, C2F5) with NOCl, NO/NO2, SO2, CO2, in the presence of caesium fluoride provide a one step synthetic route to perfluoroalkylated compounds in very good yields.

Functionalized fluoroalkyl and alkenyl silanes: Preparations, reactions, and synthetic applications

“…The silane 144 reacts with NOCl, CO 2 , SO 2 . PhNSO, and SO 2 to produce a variety of pentafluoroethyl compounds bearing sulfur and nitrogen functional groups [56]. Substitutions of phenoxy group on phosphorus and ethoxyl group on boron with pentafluoroethyl group are also successful (Scheme 38).…”

“…There have been many reports on the applications of pentafluoroethyl(trimethyl)silane 144 for not only C-C bond formation with ketones 145 [53], amide 147 (Scheme 35) [54], and aryl and alkenyl iodides 150 (Scheme 36) [55], but also carbon-heteroatom bond formations with sulfur and nitrogen reagents [56] (Scheme 37), and phosphorus [57] and boron derivatives [58] (Scheme 38). The pentavalent fluorosilicate of 144 is stable enough to react with the less reactive naphthyl iodide 151 at 100 8C (Scheme 36).…”

Electrophilic trifluoromethylation of simple inorganic salts: a one step route to trifluoromethylnitromethane, CF3NO2

“…Recently we demonstrated the application of perfluoroalkyltrimethyl silanes in the preparation of several valuable perfluoroalkylated compounds, R f NO, R f S(O)OH and R f C(O)OH in good to excellent yields from inorganic substrates, such as NOCl, NO/NO 2 , SO 2 , and CO 2 , in a manner which is much more straightforward than the traditional routes [11]. However, we were not successful in the preparation of R f NO 2 via this route although a variety of substrates were tried.…”

Conformational Properties of Ethyl- and 2,2,2-Trifluoroethyl Thionitrites, (CX3CH2SNO, X = H and F)

“…It was reported for the related alkyl nitroso compounds, RONOs, , that the perfluorination of the alkyl group leads to a stabilization of the labile functional group, but this seems not to be the case for RSNO compounds in which the stability appears to decrease with increasing electron-withdrawing effects of R. To the best of our knowledge, the only known fluorinated thionitrite, CF 3 SNO, was prepared by Mason in 1969, and its infrared and UV–vis spectra in the gas phase were interpreted in terms “of a molecule of C S symmetry, probably trans” . This preference for the anti conformer was recently confirmed by quantum chemical calculations at the B3P86/6-311+G(2df) and MP2/6-311+G(2df) level of approximations that yield an energy difference of ca.…”