Ambiphilic Properties of SF₅CF₂CF₂Br Derived Perfluorinated Radical in Addition Reactions Across Carbon–Carbon Double Bonds

Abstract

The extraordinary properties of the pentafluorosulfanyl (SF5) group attract attention of organic chemists. While numerous SF5-substituted compounds have been synthesized, the direct introduction of SF5(CF2)n moieties has remained almost unexplored. Our investigations revealed the ambiphilic character of the SF5CF2CF2 radical. Addition reactions to electron-rich or electron-deficient alkenes profit either from its electrophilic or nucleophilic properties. Thus, the readily available SF5CF2CF2Br proved to be a promising and versatile building block for the introduction of this perfluorinated moiety.

Free‐Radical Carbocyanation of Olefins

“…Radical precursors other than α‐iodo esters 1 a – c were tested, including α‐bromosulfone 7 , which proved to be less reactive than its ester counterpart, but provided the desired compound 8 in moderate yield (Scheme ). Fluorinated alkyl iodides are also competent radical precursors in these reactions, as shown by the addition of 9 a , b to olefins 2 f and 2 o , which led to 10 a – c in reasonable yields . Pyramidal C‐centered fluorinated radicals are known to add efficiently to double bonds…”

Nickel and palladium complexes with fluorinated alkyl substituted α-diimine ligands for living/controlled olefin polymerization

“…f Obtained from HT SEC-IR-η in 1,2,4-trichlorobenzene at 150°C. meters g′ ∼ 0.5 and viscosity ratio ∼2 which suggests moderately branched to linear topology ( Table 5, runs [41][42][43][44]. In contrast, PEs prepared at low ethene pressure (0.05 bar) showed a significant shift of their MH plots towards lower values of intrinsic viscosity (runs 45-48, Fig.…”

“…42,43 Consistent with standard practice in heavy fluorous chemistry, compound identity and purity were gauged from HRMS data and detailed NMR analysis. [44][45][46][47][48][49][50][51] Fourier transform infrared spectroscopy (FT-IR) measurements were performed on a NICOLET iS50R spectrometer (Thermo Scientific, USA). A Diamond ATR crystal and a DTGS detector were used for the measurements in the range of 4000-400 cm −1 .…”

Alkyl Enol Ethers: Development in Intermolecular Organic Transformation

“…When 207 treated with electron‐deficient enol ether then it behaves as a nucleophile. The compound 208 was further reacted with 2,4‐dinitrophenylhydrazine in the presence of H 3 PO 4 for the synthesis of hydrazine derivative 209 [100] …”