Electrochemical Oxidation of Polyfluoroalkyl Iodides: Direct Anodic Transformation of C8F17CH2CH2I to Amides, Esters, and Ethers

Article abstract of DOI:10.1021/jo00259a020

The cyclic voltammetry of polyfluoroalkyl iodides of the type R_fCH2CH2I (R_f = n-C6F13, n-C8F17, n-C10F21) and R_fI (R_f = n-C4F9, n-C6F13,n-C8F17, n-C10F21) was investigated in nonaqueous media.All the iodides exhibited one distinctive oxidation peak, but only C8F17CH2CH2I was suitable for surveying preparative-scale electrosynthetic reactions because the other iodides either had poor solubility or caused severe filming of the anode.The direct anodic transformations of the iodide to the corresponding amides (C8F17CH2CH2NHCOR; R = CH3, CH=CH2, C(Me)=CH2), esters (C8F17CH2CH2OCOR; R = CH3, CF3, CH=CH2, C(Me)=CH2, C6H5), ethers (mainly C8F17CH2CH2OCH2CF3), and alcohol (C8F17CH2CH2OH) were observed and a general mechanistic scheme involving a hypervalent iodanyl radical intermediate is proposed.