Side-chain fragmentation of arylalkanol radical cations. Carbon-carbon and carbon-hydrogen bond cleavage and the role of α- and β-OH groups

Enrico Baciocchi, Massimo Bietti, Lorenza Putignani, Steen Steenken

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Abstract

A product analysis and kinetic study of the one-electron oxidation of a number of 1-arylpropanols, 1,2-diarylethanols, and some of their methyl ethers by potassium 12-tungstocobaltate(III) (abbreviated as Co(III)W) in aqueous acetic acid was carried out and complemented by pulse radiolysis experiments. The oxidations occur via radical cations which undergo side-chain fragmentation involving the C(α)-H and/or C(α)-C(β) bond. With 1-(4-methoxyphenyl)-2-methoxypropane (1), only deprotonation of the radical cation is observed. In contrast, removing the ring methoxy group leads to exclusive C-C bond cleavage in the radical cation. Replacing the side-chain β-OMe by β-OH, the radical cation undergoes both C-C and C-H bond cleavage, with both pathways being base catalyzed. C-C bond breaking in the radical cation is also enhanced by an α-OH group, as shown by 1-(4-methoxyphenyl)-2,2-dimethyl-1-propanol (7), where this pathway, which is also base catalyzed, is the only one observed. Interestingly, α- and β-OH groups exhibit a very similar efficiency in assisting the C-C bond cleavage route in the radical cations, as is evident from the kinetic and products study of the oxidation of 1-phenyl-2-(4-methoxyphenyl)ethanol (5) and 1-(4-methoxyphenyl)-2-phenylethanol (6) by Co(III)W, and from pulse radiolysis experiments on 5 and 6. C-C bond cleavage is the main reaction for both radical cations which exhibit a very similar rate of fragmentation (k = 2.0 and 3.2 x 104 s-1, respectively). In both fragmentation reactions a small solvent isotope effect, k(H2O)/k(D2O) (1.4 for 5.+ and 1.2 for 6.+) and negative activation entropies are observed. These data suggest that a key role in the assistance by α- or β-OH groups to C-C bond cleavage is played by hydrogen bonding or specific solvation of these groups. The kinetic study of the oxidations promoted by Co(III)W has also shown that when only one group, OH or OMe, is present in the side chain (either on C(α) or C(β)), the fragmentation step or both the electron transfer and fragmentation steps contribute to the overall oxidation rate. However, with an OH group on both carbons of the scissile bond, as in 1-(4-methoxyphenyl)-1,2-propanediol (9), the rate of C-C bond cleavage is so fast that the electron transfer step becomes rate determining.

Original languageEnglish
Pages (from-to)5952-5960
Number of pages9
JournalJournal of the American Chemical Society
Volume118
Issue number25
DOIs
Publication statusPublished - Jun 26 1996

ASJC Scopus subject areas

  • Chemistry(all)

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