Xanthates as Thiol Surrogates for Nucleophilic Substitution with Aryl Halides

Соколов, Анатолий И.; Mikhaylov, Andrey А.; Балеева, Надежда С.; Баранов, Михаил С.

doi:10.1002/ejoc.202100647

Cited by 9 publications

(3 citation statements)

References 55 publications

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“…The addition of alkyl halides and aryl halides to xanthates may provide a general route for preparing thioethers without using odorous thiol starting materials. Baranov [34] and Kakulapati [35] reported the use of xanthates as Disclaimer/Publisher's Note: The statements, opinions, and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions, or products referred to in the content.…”

Section: Introductionmentioning

confidence: 99%

Expedient Syntheses of Alkyl and Aryl Thioethers using Xanthates as Thiol-Free Reagents

Nie,

He,

Xie

et al. 2024

Preprint

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Thioethers are critical in the fields of pharmaceuticals and organic synthesis, but most of the methods for synthesizing alkyl thioethers employ foul-smelling thiols as starting materials or generate them as by-products. Additionally, most thiols are air-sensitive and are easily oxidized to produce disulfides under atmospheric conditions; thus, a novel method for synthesizing thioethers is necessary. This paper reports a simple, effective, green method for synthesizing dialkyl or alkyl aryl thioether derivatives using odorless, stable, low-cost ROCS2K as a thiol surrogate. This transformation offers a broad substrate scope and good functional group tolerance with excellent selectivity. The reaction likely proceeds via xanthate intermediates, which can be readily generated via the nucleophilic substitution of alkyl halides or aryl halides with ROCS2K under transition-metal-free and base-free conditions.

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Section: Introductionmentioning

confidence: 99%

Expedient Syntheses of Alkyl and Aryl Thioethers using Xanthates as Thiol-Free Reagents

Nie,

He,

Xie

et al. 2024

Preprint

View full text Add to dashboard Cite

show abstract

“…The addition of alkyl halides and aryl halides to xanthates may provide a general route for preparing thioethers without using odorous thiol starting materials. Baranov [ 34 ] and Kakulapati [ 35 ] reported the use of xanthates as thiol surrogates in nucleophilic substitution or cross-coupling with aryl halides in synthesizing aryl thioethers ( Scheme 1 a,b). Karchava et al described the visible-light-driven S-arylation of EtOCS 2 K (Et = ethyl) using aryl halides in synthesizing aryl thioethers [ 36 ], followed by the reaction of diaryliodonium salts with xanthate salts to prepare the corresponding alkyl aryl thioether compounds ( Scheme 1 c) [ 37 ].…”

Section: Introductionmentioning

confidence: 99%

Expedient Synthesis of Alkyl and Aryl Thioethers Using Xanthates as Thiol-Free Reagents

Nie,

He,

Xie

et al. 2024

Molecules

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Thioethers are critical in the fields of pharmaceuticals and organic synthesis, but most of the methods for synthesis alkyl thioethers employ foul-smelling thiols as starting materials or generate them as by-products. Additionally, most thiols are air-sensitive and are easily oxidized to produce disulfides under atmospheric conditions; thus, a novel method for synthesizing thioethers is necessary. This paper reports a simple, effective, green method for synthesizing dialkyl or alkyl aryl thioether derivatives using odorless, stable, low-cost ROCS2K as a thiol surrogate. This transformation offers a broad substrate scope and good functional group tolerance with excellent selectivity. The reaction likely proceeds via xanthate intermediates, which can be readily generated via the nucleophilic substitution of alkyl halides or aryl halides with ROCS2K under transition-metal-free and base-free conditions.

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“…Thiols and disulfides are important precursors for the synthesis of a variety of pharmaceutically important sulfur-containing compounds . In recent years, many processes have appeared that allow for the introduction of a single sulfur atom or a sulfonyl group into compounds for the synthesis of free thiols and sulfinates with subsequent functionalization of the sulfur site …”

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confidence: 99%

Light-Promoted Dearylation of Perfluorinated Aryl Sulfides with N-Heterocyclic Carbene–Borane

et al. 2022

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The removal of the tetrafluoropyridinyl group tethered to a sulfur atom using a complex of N-heterocyclic carbene (NHC) with borane is described. The reaction is performed under blue light irradiation with a disulfide as radical initiator. The selective cleavage of S−Ar in preference to the weaker S−Alk bond is achieved as a result of aromatic radical substitution of the thiyl group by a NHC-stabilized boron-centered radical. Alkyl thiols, which are the primary products of the dearylation, are in situ oxidized or alkylated, affording disulfides or sulfides, respectively.

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Xanthates as Thiol Surrogates for Nucleophilic Substitution with Aryl Halides

Cited by 9 publications

References 55 publications

Expedient Syntheses of Alkyl and Aryl Thioethers using Xanthates as Thiol-Free Reagents

Expedient Syntheses of Alkyl and Aryl Thioethers using Xanthates as Thiol-Free Reagents

Expedient Synthesis of Alkyl and Aryl Thioethers Using Xanthates as Thiol-Free Reagents

Light-Promoted Dearylation of Perfluorinated Aryl Sulfides with N-Heterocyclic Carbene–Borane

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