2010/03/10 by Christos Douvris, C. M. Nagaraja, Chun‐Hsing Chen +2 · 2 citations
Chemistry · Pharmacology, Toxicology and Pharmaceutics · #Alkyl #Aryl #Bromide #Catalysis #Chemistry #Fluorine in Organic Chemistry #Halide #Halogen #Halogen bond #Halogenation #Inorganic Fluorides and Related Compounds #Medicinal chemistry #Organic chemistry #Organoboron and organosilicon chemistry #Reagent #Stoichiometry
paper · doi:10.1021/ja100605m
openalex publication_date 2010/03/10 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/09
Trialkylsilylium cation equivalents partnered with halogenated carborane anions (such as Et(3)Si[HCB(11)H(5)Cl(6)]) function as efficient and long-lived catalysts for hydrodehalogenation of C-F, C-Cl, and C-Br bonds with trialkylsilanes as stoichiometric reagents. Only C(sp(3))-halogen bonds undergo this reaction. The range of C-F bond-containing substrates that participate in this reaction is quite broad and includes simple alkyl fluorides, benzotrifluorides, and compounds with perfluoroalkyl groups attached to an aliphatic chain. However, CF(4) has proven immune to this reaction. Hydrodechlorination was carried out with a series of alkyl chlorides and benzotrichlorides, and hydrodebromination was studied only with primary alkyl bromide substrates. Competitive experiments established a pronounced kinetic preference of the catalytic system for activation of a carbon-halogen bond of a lighter halide in primary alkyl halides. On the contrary, hydrodechlorination of C(6)F(5)CCl(3) proceeded much faster than hydrodefluorination of C(6)F(5)CF(3) in one-pot experiments. A solid-state structure of Et(3)Si[HCB(11)H(5)Cl(6)] was determined by X-ray diffraction methods.