Radical ion probes. Part 10. Ceric(IV) ammonium nitrate oxidation of cyclopropylarenes†

Wang, Yonghui; Tanko, James M.

doi:10.1039/a805655b

Cited by 16 publications

(8 citation statements)

References 39 publications

(30 reference statements)

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“…250 A detailed investigation of the cation radicals of various aryl cyclopropanes generated by CAN has been reported recently. 251 A facile CAN-mediated oxidative rearrangement of alkoxyaryl cyclobutanes has been reported from our laboratory. 183 It was found that treatment of the cyclobutane 450 with CAN in dry methanol in an oxygen atmosphere led to formation of the keto methoxy product 451.…”

Section: Fragmentation Reactionsmentioning

confidence: 99%

Cerium(IV) Ammonium NitrateA Versatile Single-Electron Oxidant

2007

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He was a visiting scientist at Columbia University during 1979−82 and Visiting professor at the University of Pernambuco in Brazil in May 2001. He is a fellow of the Indian Academy of Sciences and a Silver Medalist of the Chemical Research Society of India. His research interests include cycloadditions, radical-mediated C−C and C−heteroatom bond-forming reactions, multicomponent reactions, and heterocyclic synthesis. Forty students have completed Ph.D. degrees under his supervision, and he has published nearly 200 papers in major international journals. Ani Deepthi was born in Kollam, Kerala State, India, in 1980. She obtained her B.Sc. degree from Kerala University (Fatima Mata National College, Kollam) in 2000 and her M.Sc. degree (First Rank) from the Cochin University of Science and Technology in 2002. She did her doctoral research under the guidance of Dr. Vijay Nair in the Regional Research Laboratory (CSIR) Trivandrum, working in the area of multicomponent reactions and has submitted her Ph.D. thesis to the

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Section: Fragmentation Reactionsmentioning

confidence: 99%

Cerium(IV) Ammonium NitrateA Versatile Single-Electron Oxidant

2007

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“…[145][146][147][148][149][150][151] It is the combination of these features and the conjugative effects described above that have attracted medicinal chemists to this class of molecules. On one hand, the arylcyclopropane moiety can make van der Waal's contacts just as alkyl arenes similar in size and with similar electrostatic surface potentials do.…”

Section: Discussionmentioning

confidence: 96%

Arylcyclopropanes: Properties, Synthesis and Use in Medicinal Chemistry

Gagnon

Duplessis

Fader

2010

Organic Preparations and Procedures International

108

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“…As it is well-known that arylcyclopropane radical cations can undergo a facile ring-opening reaction by nucleophilic attack at the C β carbon of the cyclopropane ring, ,− a possible mechanistic alternative is that described in paths d−f of Scheme . 3 •+ undergoes a water-induced ring-opening reaction to give a stabilized benzylic radical (path d).…”

Section: Discussionmentioning

confidence: 99%

One-Electron Oxidation of 2-(4-Methoxyphenyl)-2-Methylpropanoic and 1-(4-Methoxyphenyl)cyclopropanecarboxylic Acids in Aqueous Solution. The Involvement of Radical Cations and the Influence of Structural Effects and pH on the Side-Chain Fragmentation Reactivity

Bietti

Capone

2007

J. Org. Chem.

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A product and time-resolved kinetic study on the one-electron oxidation of 2-(4-methoxyphenyl)-2-methylpropanoic acid (2), 1-(4-methoxyphenyl)cyclopropanecarboxylic acid (3), and of the corresponding methyl esters (substrates 4 and 5, respectively) has been carried out in aqueous solution. With 2, no direct evidence for the formation of an intermediate radical cation 2*+ but only of the decarboxylated 4-methoxycumyl radical has been obtained, indicating either that 2*+ is not formed or that its decarboxylation is too fast to allow detection under the experimental conditions employed (k > 1 x 10(7) s(-1)). With 3, oxidation leads to the formation of the corresponding radical cation 3*+ or radical zwitterion -3*+ depending on pH. At pH 1.0 and 6.7, 3*+ and -3*+ have been observed to undergo decarboxylation as the exclusive side-chain fragmentation pathway with rate constants k = 4.6 x 10(3) and 2.3 x 10(4) s(-1), respectively. With methyl esters 4 and 5, direct evidence for the formation of the corresponding radical cations 4*+ and 5*+ has been obtained. Both radical cations have been observed to display a very low reactivity and an upper limit for their decay rate constants has been determined as k < 10(3) s(-1). Comparison between the one-electron oxidation reactions of 2 and 3 shows that the replacement of the C(CH3)2 moiety with a cyclopropyl group determines a decrease in decarboxylation rate constant of more than 3 orders of magnitude. This large difference in reactivity has been qualitatively explained in terms of three main contributions: substrate oxidation potential, stability of the carbon-centered radical formed after decarboxylation, and stereoelectronic effects. In basic solution, -3*+ and 5*+ have been observed to react with -OH in a process that is assigned to the -OH-induced ring-opening of the cyclopropane ring, and the corresponding second-order rate constants (k-OH) have been obtained. With -3*+, competition between decarboxylation and -OH-induced cyclopropane ring-opening is observed at pH >or=10, with the latter process that becomes the major fragmentation pathway around pH 12.

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Radical ion probes. Part 10. Ceric(IV) ammonium nitrate oxidation of cyclopropylarenes†

Cited by 16 publications

References 39 publications

Cerium(IV) Ammonium NitrateA Versatile Single-Electron Oxidant

Cerium(IV) Ammonium NitrateA Versatile Single-Electron Oxidant

Arylcyclopropanes: Properties, Synthesis and Use in Medicinal Chemistry

One-Electron Oxidation of 2-(4-Methoxyphenyl)-2-Methylpropanoic and 1-(4-Methoxyphenyl)cyclopropanecarboxylic Acids in Aqueous Solution. The Involvement of Radical Cations and the Influence of Structural Effects and pH on the Side-Chain Fragmentation Reactivity

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