Formation of Cyclic Sulfinates and Sulfinamides through Homolytic Substitution at the Sulfur Atom

Coulomb, J; Certal, Victor; Fensterbank, Louis; Lacôte, Emmanuel; Malacrìa, Max

doi:10.1002/anie.200503369

Cited by 73 publications

(39 citation statements)

References 37 publications

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“…1e4 While examples can be found of alkyl, aryl, and acyl radicals undergoing this chemistry at the sulfur atom in sulfides, 2e4 sulfoxides, 5e9 sulfinates, 10,11 and sulfinamides, 10,11 to the best of our knowledge there are no examples reported for this chemistry involving sulfones. 7e9 The examples depicted in Scheme 1 illustrate the versatility of this chemistry; radicals derived from acylselenides (e.g., 1), aryl and alkyl bromides (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…7e9 The examples depicted in Scheme 1 illustrate the versatility of this chemistry; radicals derived from acylselenides (e.g., 1), aryl and alkyl bromides (e.g. 2, 3) afford thiolactones, 12 cyclic sulfoxides, 5 and sultines 10,11 in good yield.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we showed that cyclic sulfinates and sulfonamides could be prepared utilizing this chemistry, 10,11 and more recently that computational chemistry provided valuable insight into the intimate mechanistic details of the key bond-forming and bondbreaking steps. 16 With an inherent interest in homolytic substitution reactions involving selenium and their further development, 17 we chose …”

Section: Introductionmentioning

confidence: 99%

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7-Selenabicyclo[2.2.1]heptane

et al. 2012

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a b s t r a c tAb initio and density functional theory (DFT) calculations predict that intramolecular homolytic substitution by alkyl radicals at the selenium atom in seleninates proceeds through smooth transition states in which the attacking and leaving radicals adopt a near collinear arrangement. When forming a fivemembered ring and the leaving radical is methyl, G3(MP2)-RAD calculations predict that this reaction proceeds with an activation energy (DE 1 z ) of 30.4 kJ mol . Homolytic addition to the phenyl group was found not to be competitive with substitution, with a calculated barrier of 57.6 kJ mol À1. This computational study provides insight into homolytic substitution chemistry involving seleninates.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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7-Selenabicyclo[2.2.1]heptane

et al. 2012

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“…Examples can be found of alkyl, aryl, and acyl radicals undergoing this chemistry efficiently at the sulfur atom in sulfides, 5 sulfoxides, 12,22,23 sulfinates, [24][25][26] and sulfonamides, [24][25][26] but not at sulfones. 22,27 Scheme 7 illustrates the application of this chemistry to the preparation of the dihydrobenzothiophene-containing tocopherol-like antioxidant (2); α-tocopherol is the main component of vitamin E. In the key step, aryl radical (3), generated under standard conditions, was able to undergo homolytic substitution at sulfur; subsequent deprotection gave 5-hydroxy- (2) in 62% yield over two steps.…”

Section: Ring Closures At Sulfurmentioning

confidence: 99%

“…24,25 As shown in Scheme 11, a number of variables were explored during their investigation; these included the nature of the (precursor) halide (X), the nature of the aryl ring (Y), the substitution (Z) on the tether, as well as the nature of the leaving radical (LG).…”

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Intramolecular Homolytic Substitutions in Synthesis

Kyne

Schiesser

2012

Encyclopedia of Radicals in Chemistry, Biology and Materials

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Intramolecular homolytic substitution chemistry offers the synthetic practitioner efficient and convenient methods for the preparation of higher heterocycles that complement existing ionic processes, especially for the preparation of ring systems containing sulfur and selenium, as well as silicon. This article details fundamental principles and important kinetic data for intramolecular homolytic substitution chemistry involving main group heteroatoms and provides examples and illustrative procedures for the application of this chemistry to the preparation of interesting molecules, some of which are of biological significance.

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Advances in Free Radical Reactions of Organoselenium and Organotellurium Compounds

Press

Back²

2011

Patai's Chemistry of Functional Groups

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Free radical reactions of organoselenium and tellurium compounds have been widely studied and exploited since the first two volumes of this series appeared. Alkyl aryl selenides and tellurides undergo alkyl C‐Se or C‐Te cleavage with stannanes or silanes to generate alkyl radicals that can be employed in reductions, allylations and both intermolecular and intramolecular additions to a large variety of unsaturated substrates, terminated by either hydrogen or arylchalcogen transfer. Selenoesters, telluroesters and related species generate acyl radicals that are useful in overall decarboxylations of carboxylic acids, and in addition and radical cyclization processes, including cascade reactions of polyenes to afford polycyclic products. Homolytic cleavage of diselenides and ditellurides produces selenyl and telluryl radicals that can be employed in additions to unsaturated acceptors, while the dichalcogenides themselves function as effective trapping agents for radicals produced in a variety of other ways, as from Barton thiohydroxamates. Selenols are efficient hydrogen donors that are of importance in kinetic studies of radical processes. When selenium and tellurium are joined to other heteroatoms, the resulting reagents effect radical 1,2‐additions to unsaturated substrates, as in the case of selenosulfonation and azidoselenenylation reactions. Other radical processes include oxidations, S H 2 substitutions, single electron transfers, extrusions and fragmentations, and reactions performed on solid supports. The synthetic utility of these processes, as well as mechanistic considerations are covered in this chapter.

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Formation of Cyclic Sulfinates and Sulfinamides through Homolytic Substitution at the Sulfur Atom

Cited by 73 publications

References 37 publications

7-Selenabicyclo[2.2.1]heptane

7-Selenabicyclo[2.2.1]heptane

Intramolecular Homolytic Substitutions in Synthesis

Advances in Free Radical Reactions of Organoselenium and Organotellurium Compounds

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