Solvent dependent reductive defluorination of aliphatic C–F bonds employing Sm(HMDS)2

Abstract

Sm(HMDS)(2) in n-hexane mediates fast cleavage of primary, secondary and tertiary alkyl fluorides in good to excellent yields. In n-hexane Sm(HMDS)(2) exhibits uniquely enhanced reductive ability towards the C-F bond compared to when using THF as solvent.

O‐Trifluoromethylation of N,N‐Disubstituted Hydroxylamines with Hypervalent Iodine Reagents

“…To verify this hypothesis experimentally, we conducted the reaction in neat styrene to force the addition of the CF 3 radical to the double bond. Analysis of the reaction mixture by 19 F NMR spectroscopy showed the expected product of the radical β‐trifluoromethylation of styrene13 formed in 126 % yield on the basis of 19 F NMR spectroscopy with respect to dibenzylhydroxylamine in addition to the desired product (26 % yield).…”

Selective CF Bond Activation: Substitution of Unactivated Alkyl Fluorides using YbI3

“…During recent studies of reductive cleavage of CF bonds with Sm(HMDS) 2 (HMDS=hexamethyldisilazide), we discovered that traces of alkyl iodides could be detected in the reaction mixtures 8. Encouraged by this finding we turned our attention to trivalent lanthanides.…”

Selective CF Bond Activation: Substitution of Unactivated Alkyl Fluorides using YbI3

“…During recent studies of reductive cleavage of CÀF bonds with Sm(HMDS) 2 (HMDS = hexamethyldisilazide), we discovered that traces of alkyl iodides could be detected in the reaction mixtures. [8] Encouraged by this finding we turned our attention to trivalent lanthanides. 1-Fluorodecane (1 a) was exposed to SmI 3 in THF at room temperature.…”