Cation radical cycloadditions and related sigmatropic reactions

Bauld, Nathan L.

doi:10.1016/s0040-4020(01)89486-2

Cited by 315 publications

(163 citation statements)

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“…1,5,20 Unactivated olefins are considerably more difficult to oxidize, having potentials that significantly exceed the literature "limit" [16][17][18] of a 500 mV differential with the E1/2 potential of magic green. We were surprised, therefore, when we observed that cis-cyclooctene (cis-COE), cis-3, with a nominal oxidation potential of 1.85 V (vide infra) underwent cyclobutanation in the presence of catalytic amounts of in-situ generated [ReCp(CO)3] + (2 + Cp =  5 -C5H5), which has a potential of only 1.16 V vs FcH in CH2Cl2.…”

Section: ------------------------------------------------------------mentioning

confidence: 94%

“…This process may be triggered by either oneelectron oxidation (Scheme 1) 1 or by photochemical excitation of the olefin. 2 Originally reported by Ledwith 3 , this reaction was developed primarily by Bauld and co-workers, 1,4,5 who extended it to include radical-induced Diels-Alder reactions. 1,5 Compared to strictly thermal reactions of the neutral olefins and diolefins, the rates of both [2 + 2] and [2 + 4] coupling reactions are enormously accelerated by radical cation initiation.…”

Section: Introductionmentioning

confidence: 99%

“…2 Originally reported by Ledwith 3 , this reaction was developed primarily by Bauld and co-workers, 1,4,5 who extended it to include radical-induced Diels-Alder reactions. 1,5 Compared to strictly thermal reactions of the neutral olefins and diolefins, the rates of both [2 + 2] and [2 + 4] coupling reactions are enormously accelerated by radical cation initiation. 6,7 For reasons to be discussed below, application of this reaction has been largely restricted to "activated" olefins having comparatively low oxidation potentials.…”

Section: Introductionmentioning

confidence: 99%

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Electron-transfer catalyzed cycloaddition reactions of unactivated cyclic olefins in weakly coordinating anion electrolyte

Stewart

Lam

Chong

et al. 2015

Journal of Electroanalytical Chemistry

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mechanism appears to involve a key propogation step in which an olefin radical cation reacts with a neutral olefin to give a cyclobutyl radical cation, which then, accepts an electron, most likely from another olefin, to form the final neutral compound. Although the E1/2 potentials of the ET mediators are 660-900 mV lower than the estimated oxidation potentials of the olefins, the endergonic nature of the ET initiation step works to the advantage of the chain process by favoring a radical-substrate propogation step.3

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Section: ------------------------------------------------------------mentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron-transfer catalyzed cycloaddition reactions of unactivated cyclic olefins in weakly coordinating anion electrolyte

Stewart

Lam

Chong

et al. 2015

Journal of Electroanalytical Chemistry

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“…In the domain of radical chains triggered by electron transfer, let us also quote Diels-Alder reactions (types of [2 + 2] and [2 + 4] developed by Bauld through the oxidizing induction brought by cation radicals [30] as sources of four and six-membered rings and already fully developed in purely organic synthesis as symbolized by Scheme 1.6). Let us note that the reaction is formally induced by [1 + 2] or [1 + 4] additions.…”

Section: Triggering Of Radical Chains Via Electro-chemical Activationmentioning

confidence: 99%

“…Let us note that the reaction is formally induced by [1 + 2] or [1 + 4] additions. In electro-chemistry, the triggering of chains was first induced by electro-generated cation radicals [30,31].…”

Section: Triggering Of Radical Chains Via Electro-chemical Activationmentioning

confidence: 99%

How to Modify Solid Electrodes for Generating New Interfacial Processes — Another Approach in Electro-Chemical Catalysis

Simonet¹

2017

Catalytic Science Series

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The word "catalytic" comes from Ancient Greek and can be translated as "a breaking down". The word "catalysis" was introduced in the first half of the 19 th century by the Swedish Scientist J. J. Berzelius who applied it to the observation that in chemical reactions, the normal barriers can be removed by the help of external reagents. Nowadays, the term "catalysis" remains attached to the petroleum refining science introduced more than half a century ago. It mainly refers to the removal of sulfur and nitrogen from naphthas in order to produce fuel (gasoline, diesels, etc.). Refining reactions are conducted in the presence of catalysts often constituting of metals and metal oxides (mixed metal oxides, MMOs) in order to decrease cracking temperatures and improve selectivity of chemical reactions [1,2].In electro-chemistry, the term catalysis is quite recent and remains mainly linked to an easiness in interfacial reactions. Therefore, for It may then appear that most of the 19 chapters that follow this introduction possess an undeniable character of novelty both in the domain of new catalytic reactions, the chemical and electrochemical modifications of conducting solid surfaces, especially in the field of carbons, precious metals and copper. It is obvious however that some parts of the book could present a superficial or unbelievable aspect since both the ideas and the significant results do not go sufficiently into enough details about the scientific aspect and the possible applications. It could actually be the responsibility of the reader to freely reproduce some results and use some ideas (good or judged as incomplete) presented in this research.Among the well-established electro-catalytic processes, redox catalysis remains an intriguing and powerful method that specifically belongs to organic electro-chemistry. This technique 3 corresponds to the innovative and important progress in the field of indirect electrolyses. The first evidence of the indirect reduction of an alkyl-halide RX by the anion radical of naphthalene was reported by Fry [3] while the wide scope of redox catalysis (kinetics and synthetic applications) was unambiguously disclosed by Lund and co-workers [4-6, 8, 16] in the course of 1970s by using polarographic currents of Koutecky's theory. Meanwhile, other authors were also interested in this form of catalysis [7,9,10]. Based on this indirect process, kinetic and thermodynamic results were successfully achieved by by using the voltammetric technique. Thus, for the first time, thermodynamic data and standard potential values concerning reduction of R • radicals (issued from the cleavage of alkyl and aryl halides, (RX's and ArX's)) were appreciated in this way. Thus, RIs (alkyl iodides) in general and certain RBrs (alkyl bromides) may lead to one-electron scissions at cathodes. Therefore, selective one-electron processes and subsequently produced free radicals were considered to be of high interest also for synthesis and they prompted many authors in the course of last three decades to revi...

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Cation radical chain cycloaddition polymerization and cationic macrocyclopolymerization

Bauld

Gao

2000

Polym. Int.

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Cation radical cycloadditions and related sigmatropic reactions

Cited by 315 publications

References 94 publications

Electron-transfer catalyzed cycloaddition reactions of unactivated cyclic olefins in weakly coordinating anion electrolyte

Electron-transfer catalyzed cycloaddition reactions of unactivated cyclic olefins in weakly coordinating anion electrolyte

How to Modify Solid Electrodes for Generating New Interfacial Processes — Another Approach in Electro-Chemical Catalysis

Cation radical chain cycloaddition polymerization and cationic macrocyclopolymerization

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