Functionalization of saturated fluorocarbons

Functionalization of saturated fluorocarbons with and without light

“…As was found in the earlier work [10], perfluoro-1,3-dimethylcyclohexane (12) underwent functionalization only once despite the presence of two tertiary sites. Apparently the enolate's negative charge suffices to protect the ion from attack at the other vulnerable position.…”

“…Enolate 5 reacted nearly quantitatively at RT with methyl triflate to yield enol ether 8 [10,14] (Scheme 4), which was isolated by preparative GC in 52% yield based on fluorocarbon 1. In similar fashion, perfluoromethylcyclopentane (9) was transformed in high yield into enolate 10 [10], which was methylated to give enol ether 11 [15].…”

“…In similar fashion, perfluoromethylcyclopentane (9) was transformed in high yield into enolate 10 [10], which was methylated to give enol ether 11 [15]. Interestingly, bdiketonate ion 7 failed to react at RT with methyl triflate, revealing it to be a remarkably weak nucleophile.…”

“…Although functionalization without aromatization has been achieved in other ways [3,7,9], several years ago we developed the only general method that introduces a functional group in good yields and without extensive loss of fluoride into saturated fluorocarbons having tertiary sites [10]. Its secret of success is interception by hydroxide ion of an early intermediate in the reduction cascade, with the formation of an enolate ion.…”

Conversion of Carbon–Fluorine Bonds α to Transition Metal Centers to Carbon–Hydrogen, Carbon–Carbon, and Carbon–Heteroatom Bonds

“…In contrast, the selective reductive activation of saturated fluorocarbons is rather rare; [126] in one case reduction was stopped at the fluoroalkene stage by chemical interception to give a stable enolate. [127] Activation of Carbon-Fluorine Bonds α to Transition Metal Centers Stable transition metal organometallic compounds containing fluoroalkyl ligands have been known since the halcyon days of organotransition metal chemistry, [128][129][130][131][132] and an early report indicated that their C-F bonds were reactive towards acids (and bases). [133] Not surprisingly, the first complexes of transition metals with tetrafluoroethylene ligands were prepared by chemists at DuPont, [134][135] and it was quickly realized that the structure of the M(η 2 -C 2 F 4 ) fragment resembled that of a saturated metallacyclopropane, with extensive rehybridization of the C-F bonds to acquire more p character.…”