Topologically Controlled Coulombic Interactions, a New Tool in the Developing of Novel Reactivity. Photochemical and Electrochemical Cleavage of Phenyl Alkyl Ethers

Electrostatic effects on the photoreactions of nitrophenyl ethers with nucleophiles

“…The electroreductive behavior of these compounds has been previously reported by us. 2,20 Cyclic voltamograms show in all the cases a reversible first wave that indicates the radical anion is stable in the time scale of cyclic voltammetry. A small shift of the standard potential Eº of the couple substrate/radical anion or substrate/zwiterionic radical is observed when comparing 4-nitroveratrole (1) (-1.13 V vs. SCE) and the tetrafluoroborate of N-methyl-N-(2-(2-methoxy-4-nitrophenoxy)ethyl)piperidinium (3) …”

“…The "Topologically Controlled Coulombic Interactions (TCCI) Effect" has been introduced and used by us to achieve some previously unknown processes in some cases (i.e reductive cleavage of nitrophenyl alkyl ethers), [1][2][3] and to alter the normal reductive reactivity in others (i.e regioselectivity change in the reductive cleavage of alkyl phenyl ethers). 4,5 This effect involves the altering of the normal behavior of a negatively charged intermediate by specifically placing a positive charge in its structure [i.e.…”

Photochemical, Electrochemical and Enzymatic Methods for Ether‐Bond Cleavage

“…Marquet [5] has reported that an electrochemical method can be applied to confirm the mechanism of a photochemical process, namely the cleavage of some phenyl alkyl ethers. The problemwas solved by preparative electrolyses of 4-nitroveratrole (38) Compounds 38 and 40 were found to be stable under the reaction conditions but 39 underwent reductive cleavage to give phenol in 39 % yield.…”

“…The TCCI effect as a new tool in the study of photochemical and electrochemical cleavage of phenyl alkyl ethers is discussed in more detailed in ref. [5] Marquet and Melloni [64] have studied the electrochemically promoted cleavage of alkyl 2,6-diphenylphenyl ethers (Scheme 15) and have shown that the preparative electrolysis of 2,6-diphenylanisole (41) in THF solution at controlled potential (-2.6 V vs. SCE) gives only a trace of m-diphenyl 42 (dealkoxylation). No 2,6-diphenylphenol (dealkylation) is produced, whereas the electrolysis in DMF affords a 29 % yield of 2,6-diphenylphenol (dealkylation).…”

“…[4,5] It is known that phenyl ethers substituted by electron-attracting groups do not undergo reductive fragmentation. However, related 4-substituted phenyl ethers linked through a methylene chain to a tertiary amine give either alkyl ether photocleavage when the linker between the redox centers is short (two CH 2 groups, 1) or reduction when the linker is long (five CH 2 groups).…”