Bunte Salt CH<sub>2</sub>FSSO<sub>3</sub>Na: An Efficient and Odorless Reagent for Monofluoromethylthiolation

Liu, Fanmin; Jiang, Lvqi; Qiu, Huangyao; Yi, Wen‐Bin

doi:10.1021/acs.orglett.8b02753

Cited by 35 publications

(15 citation statements)

References 56 publications

(24 reference statements)

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“…The monofluoromethylthio moiety (SCH 2 F) widely exists in a variety of biologically active compounds (Supplementary Fig. 1 ) 44 , 45 . Previous reports to achieve aldehydic C–H monofluoromethylthiolation relied on the use of stoichiometric oxidants such as 2,2′-azodi(2-methylbutyronitrile) (AMBN) 46 or PhI(O 2 CCF 3 ) 2 /NaN 3 17 .…”

Section: Resultsmentioning

confidence: 99%

Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents

et al. 2021

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While aldehydes represent a classic class of electrophilic synthons, the corresponding acyl radicals are inherently nucleophilic, which exhibits umpolung reactivity. Generation of acyl radicals typically requires noble metal catalysts or excess oxidants to be added. Herein, we report a convenient and green approach to access acyl radicals, capitalizing on neutral eosin Y-enabled hydrogen atom transfer (HAT) photocatalysis with aldehydes. The generated acyl radicals underwent SOMOphilic substitutions with various functionalized sulfones (X–SO2R’) to deliver value-added acyl products. The merger of eosin Y photocatalysis and sulfone-based SOMOphiles provides a versatile platform for a wide array of aldehydic C–H functionalizations, including fluoromethylthiolation, arylthiolation, alkynylation, alkenylation and azidation. The present protocol features green characteristics, such as being free of metals, harmful oxidants and additives; step-economic; redox-neutral; and amenable to scale-up assisted by continuous-flow technology.

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Section: Resultsmentioning

confidence: 99%

Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents

et al. 2021

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“…Finally, in 2018 the group of Yi described the synthesis of the Bunte salt FCH2SSO3Na 8 for the installation of the SCH2F residue (Scheme 3. . This motif was introduced onto anilines through the in situ formation of the corresponding diazonium salts [45]. This transformation demonstrated an excellent scope, various functionalities were tolerated and heteroaromatic derivatives were compatible.…”

Section: The Sch2f Motifmentioning

confidence: 99%

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

Besset¹,

Poisson²

2020

Emerging Fluorinated Motifs

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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.

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“…Moreover, disubstituted aniline and trisubstituted aniline could also be converted to the corresponding products in moderate yields ( 2 i – 2 k ). In our previous work of monofluoromethylthiolation, 1‐monofluoromethyl‐thio‐3,4,5‐trimethoxybenzene could only be detected by GC‐MS and decomposed quickly, while its monofluoromethylseleno analogue 2 k was stable, no decomposition was observed even after more than three months of storage on a shelf at ambient temperature. It indicated that SeCFH 2 ‐containing compounds were more stable than their SCFH 2 analogues.…”

Section: Figurementioning

confidence: 99%

Synthesis of Monofluoromethyl Selenoethers of Aryl and Alkyl from Organoselenocyanate via One‐Pot Reaction

Cao

Jiang

2019

Adv Synth Catal

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The first practical and feasible approach for the monofluoromethylselenolation of aryl and alkyl halides via one-pot multistep synthesis using KSeCN and ICFH 2 is described. Good yields and broad functional group compatibility were obtained. The successful preparation of monofluoromethylselenolated drug-like compounds good practicability of this method. This protocol offered a number of new monofluoromethyl selenoethers, which would accelerate the use of such compounds in the areas of life science.

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Bunte Salt CH₂FSSO₃Na: An Efficient and Odorless Reagent for Monofluoromethylthiolation

Cited by 35 publications

References 56 publications

Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents

Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents

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

Synthesis of Monofluoromethyl Selenoethers of Aryl and Alkyl from Organoselenocyanate via One‐Pot Reaction

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Bunte Salt CH2FSSO3Na: An Efficient and Odorless Reagent for Monofluoromethylthiolation

Cited by 35 publications

References 56 publications

Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents

Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents

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

Synthesis of Monofluoromethyl Selenoethers of Aryl and Alkyl from Organoselenocyanate via One‐Pot Reaction

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Bunte Salt CH₂FSSO₃Na: An Efficient and Odorless Reagent for Monofluoromethylthiolation

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