Stereoselective Radical Aryl Migration Reactions from Sulfur to Carbon

Bossart, Martin; Fässler, Roger; Schoenberger, Jan; Studer, Armido

doi:10.1002/1099-0690(200208)2002:16<2742::aid-ejoc2742>3.0.co;2-r

Cited by 34 publications

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“…We then examined the case of alkyl radicals ( Table 3). The reaction of tolylsulfinates only afforded reduced material, as also reported by Studer et al [37] Presumably, the expulsion of a high-energy aryl radical would be disfavored and this energetic gap would account for the lack of cyclization. Nonetheless, the tert-butyl sulfinates worked well.…”

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confidence: 99%

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

et al. 2006

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Ring road: Cyclic sulfinates and sulfinamides can be synthesized by homolytic substitution to give alkyl and benzofused families of compounds. The presence of an additional heteroatom in the ring allows the preparation of sulfur‐based heterocycles that are useful synthetic intermediates (see scheme). The stereogenic sulfur atom transfers its chirality to prochiral radicals. TTMSS=tris(trimethylsilyl)silane, AIBN=azobisisobutyronitrile.

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

et al. 2006

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“…Thus, the very same factor that facilitated the cyclization before (breaking a more fragile bond) would now be a handicap to the cyclization, because the BDE gain was now lower. Indeed, p ‐tolyl sulfinates did not undergo cyclization, providing only reduced material (Table 6, entry 1) 26. Despite this shortcoming, the reactions of the tert ‐butyl substrates were smooth enough to give access to interesting five‐membered heterocyclic structures.…”

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confidence: 99%

Intramolecular Homolytic Substitution of Sulfinates and Sulfinamides

Coulomb

Certal

Larraufie

et al. 2009

Chemistry A European J

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A general and efficient method for the synthesis of cyclic sulfinates and sulfinamides based on intramolecular homolytic substitution (S(H)i) at the sulfur atom by aryl or alkyl radicals is described. Both alkyl and benzofused compounds can be accessed directly from easily prepared acyclic precursors. Enantiomerically enriched sulfur-based heterocycles were formed through an S(H)i process with inversion of configuration at the sulfur atom. Cyclization of prochiral radicals proceeded with varying stereochemical outcomes, depending on the size of the incoming radical. 2-Pyridyl and 2-quinolyl radicals led to biaryl compounds, which result from attack onto the ortho position of the arylsulfinate rather than a thiophilic substitution.

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“…Taking into consideration the feasibility of desulfonylative rearrangement of arene sulfonamides via 1,4-and 1,5-aryl migration from sulfur to aryl radicals, sulfonates and their variants were also studied to achieve selective C−C bond formation. [402][403][404][405][406][407][408][409][410]518 Until now, the only example of 1,4-aryl migration from sulfone to an sp 2 alkenyl radical is a photoreaction. 519 In this regard, an effort to further expand the scope of tandem radical Smiles rearrangement was made by Stephenson and co-workers (Scheme 143A).…”

Section: Radical-mediated Desulfonylation Of Sulfonates Via O−s Bond ...mentioning

confidence: 99%

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

et al. 2021

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As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for the efficient construction of diverse molecular architectures by taking advantage of their incredible reactive flexibility. Currently, their involvement in radical transformations, in which the sulfonyl group typically acts as a leaving group via selective C−S, N−S, O−S, S−S, and Se−S bond cleavage/ functionalization, has facilitated new bond formation strategies which are complementary to classical two-electron cross-couplings via organometallic or ionic intermediates. Considering the great influence and synthetic potential of these novel avenues, we summarize recent advances in this rapidly expanding area by discussing the reaction designs, substrate scopes, mechanistic studies, and their limitations, outlining the state-of-the-art processes involved in radical-mediated desulfonylation and related transformations. With a specific emphasis on their synthetic applications, we believe this review will be useful for medicinal and synthetic organic chemists who are interested in radical chemistry and radical-mediated desulfonylation in particular. CONTENTS

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Stereoselective Radical Aryl Migration Reactions from Sulfur to Carbon

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 34 publications

References 0 publications

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

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

Intramolecular Homolytic Substitution of Sulfinates and Sulfinamides

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

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