Facile synthesis of α,α-difluoroalkyl aryl thioethers and their oxidative desulfurization–fluorination to trifluorides

Hugenberg, Verena; Haufe, Günter

doi:10.1016/j.jfluchem.2010.06.010

Cited by 16 publications

(12 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(Table 3). The reaction with the p-methoxy substituted sulfide (entry 5), however, did not proceed selectively [99].…”

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 96%

“…The suggested mechanism of the formation of the alkyl-2-arylthio-2,2-difluoroacetates 92 involves two fluoro-Pummererlike rearrangements [99]. The conversion of ethyl 3-(arylthio)propionate (93) having a CH 2 -group between the reaction center and the ester group with 3 equiv of DBH and 6 equiv of Olah's reagent did not lead to ethyl 3-arylthio-3,3-difluoropropionate.…”

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 99%

“…The reaction of the b-fluorinated alkyl aryl sulfide 98 with DBH and Olah's reagent gave a mixture of the trifluoride 99, the dibromodifluoride 100 and the trifluorinated sulfide 101 in a ratio of 1:1.2:2 (Scheme 38) [99].…”

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 99%

“…These results showed that neither the electron-withdrawing effect of an ester group nor that of a fluorine atom in b-position to the reactive center is sufficient to prevent the desulfurization step, but decelerated the reaction rate and directed the reaction toward oxidative desulfurization-difluorination and desulfurizationpolybromination [99]. (Table 4, entries 1-4) [101].…”

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 99%

“…The use of NCS as an electrophile avoided the formation of the chlorodifluoride 139b (X = Cl). Depending on the substituents of the arylthio group, the reaction was possible with lower amounts of fluorinating reagent and in shorter reaction time (Table 7) [99]. This method might be developed to an appropriate method for 18 F-labeling of medicinally relevant ligands for the positron emission tomography (PET).…”

Section: Hiyama Et Al Converted Aa-difluoro(methylthio)methylmentioning

confidence: 99%

See 4 more Smart Citations

Fluoro-Pummerer rearrangement and analogous reactions

Hugenberg

Haufe

2012

Journal of Fluorine Chemistry

Self Cite

View full text Add to dashboard Cite

“…(Table 3). The reaction with the p-methoxy substituted sulfide (entry 5), however, did not proceed selectively [99].…”

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 96%

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 99%

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 99%

Section: Application Of Oxidants and Nucleophilic Fluorinating Reagentsmentioning

confidence: 99%

Section: Hiyama Et Al Converted Aa-difluoro(methylthio)methylmentioning

confidence: 99%

See 3 more Smart Citations

Fluoro-Pummerer rearrangement and analogous reactions

Hugenberg

Haufe

2012

Journal of Fluorine Chemistry

Self Cite

View full text Add to dashboard Cite

Extension to the SCF ₂ H , SCH ₂ F , and SCF ₂ R Motifs ( R = PO ( OEt ) ₂

Besset¹,

Poisson²

2020

Emerging Fluorinated Motifs

View full text Add to dashboard Cite

In this chapter, the recent and most significant progress made for the access to SCF2H, SCH2F, SCF2PO(OEt)2, SCF2COR, and SRf will be highlighted. The SCF2H MotifOver the last years, a strong interest was paid to the SCF2H group. Indeed, due to its unique properties such as a its lipophilicity, its H-bonding ability [4] and due to the presence of a more acidic proton compared with the one in the CF2H group, the development of new approaches for its introduction onto various classes of compounds was reported. Two main strategies were depicted, namely 1) the difluoromethylation of sulfur-containing molecules and 2) the direct C-SCF2H bond construction. In this section will be reported the most relevant advances made since 2016 [5]. Construction of the SCF2H MoietyDue to the importance of the SCF2H group, various strategies were elaborated to build up a S-CF2H bond. Until 2016, the use of difluorocarbene precursors was the main approach. Alternatives based on electrophilic and nucleophilic reagents or CF2H radical precursors were promising, although still in their infancy. A summary of the main reagents used in these transformations is depicted in the Scheme 3.6-1 [5]. Scheme 3.6-1 State of the art: reagents used for the difluoromethylation of sulfur-containing molecules until 2016.In this section, will be described the recent advances made since 2016 to construct a S-CF2H bond.In 2017, the group of Fu developed a methodology for the difluoromethylation of thiophenols under visible light photocatalysis [6]. Using the readily available difluorobromoacetic acid as a difluorocarbene precursor and an iridium complex as photocatalyst, a panel of thiophenols bearing halogens, ester, nitro as functional groups was functionalized in moderate to high yields (Scheme 3.6-2a). Note that even the difluoromethylation of 2-pyridinethiol was smoothly achieved . Scheme 3.6-2 Difluoromethylation of thiophenols under visible light photocatalysis.Another difluorocarbene precursor, namely the diethyl bromodifluoromethylphosphonate, was also used in combination with thiourea as the sulfur source [7]. With this system, Yi and coworkers successfully functionalized in a one-pot three-step sequence, a panel of heteroaromatic compounds (indoles, pyrroles) and electron-rich arenes (Scheme 3.6-3).Scheme 3.6-3 Difluoromethylation of heteroaromatic compounds and electron-rich arenes using diethyl bromodifluoromethylphosphonate and thiourea.

show abstract

ChemInform Abstract: Facile Synthesis of α,α‐Difluoroalkyl Aryl Thioethers and Their Oxidative Desulfurization—Fluorination to Trifluorides.

Hugenberg

Haufe

2010

ChemInform

View full text Add to dashboard Cite

Facile Synthesis of ,-Difluoroalkyl Aryl Thioethers and Their Oxidative Desulfurization-Fluorination to Trifluorides. -Difluoroacetates (II) are synthesized via two succeeding fluoro-Pummerer rearrangements using the combination of N-haloimides as electrophiles and excess Olah's reagent as the fluoride source. Subsequent treatment of (II) with the same reagents at elevated temperature gives alkyl trifluoroacetates (III) by oxidative desulfurization-fluorination. Thioethers with a CH 2 -group between reaction center and ester group do not give the corresponding difluoropropionates. -(HUGENBERG, V.; HAUFE*, G.; J. Fluorine Chem. 131 (2010) 9, 942-950, http://dx.

show abstract

Facile synthesis of α,α-difluoroalkyl aryl thioethers and their oxidative desulfurization–fluorination to trifluorides

Cited by 16 publications

References 45 publications

Fluoro-Pummerer rearrangement and analogous reactions

Fluoro-Pummerer rearrangement and analogous reactions

Extension to the SCF ₂ H , SCH ₂ F , and SCF ₂ R Motifs ( R = PO ( OEt ) ₂

ChemInform Abstract: Facile Synthesis of α,α‐Difluoroalkyl Aryl Thioethers and Their Oxidative Desulfurization—Fluorination to Trifluorides.

Contact Info

Product

Resources

About

Facile synthesis of α,α-difluoroalkyl aryl thioethers and their oxidative desulfurization–fluorination to trifluorides

Cited by 16 publications

References 45 publications

Fluoro-Pummerer rearrangement and analogous reactions

Fluoro-Pummerer rearrangement and analogous reactions

Extension to the SCF 2 H , SCH 2 F , and SCF 2 R Motifs ( R = PO ( OEt ) 2

ChemInform Abstract: Facile Synthesis of α,α‐Difluoroalkyl Aryl Thioethers and Their Oxidative Desulfurization—Fluorination to Trifluorides.

Contact Info

Product

Resources

About

Extension to the SCF ₂ H , SCH ₂ F , and SCF ₂ R Motifs ( R = PO ( OEt ) ₂