Synthesis of Monofluoromethylthioesters from Aldehydes

Guo, Shi‐Huan; Wang, Meng-Yue; Pan, Gao‐Fei; Zhu, Xue‐Qing; Gao, Ya‐Ru; Wang, Yongqiang

doi:10.1002/adsc.201800136

Cited by 28 publications

(19 citation statements)

References 68 publications

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“…In the presence of radical-clock type reagent, the ring-closure product was isolated (81b). Based on these preliminary results and previous literature, 145,[183][184][185][186][187][188][189][190] we proposed a radical mechanism, in which the difluoromethylthiyl radical was generated from either the homolysis event of…”

Section: Photo-induced C Sp2 -H Difluoromethylthiolation: Synthesis Omentioning

confidence: 58%

Exploration of new reaction tools for late-stage functionalization of complex chemicals

et al. 2019

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Chemistry has always had as a target the conversion of molecules into valuable materials. Nevertheless, the aim of past synthesis has primarily focused on achieving a given transformation, regardless of the environmental impact of the synthetic route. Given the current global situation, the demand for sustainable alternatives has substantially increased. Our group focuses on developing selective chemical transformations that benefit from mild conditions, improved atom economy, and that can make use of renewable feedstocks as starting materials. This account summarizes our work over the past two decades specifically regarding the selective removal, conversion, and addition of functional groups that can, later on, be applied at a late stage for the modification of complex molecules.

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Section: Photo-induced C Sp2 -H Difluoromethylthiolation: Synthesis Omentioning

confidence: 58%

Exploration of new reaction tools for late-stage functionalization of complex chemicals

et al. 2019

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“…The products were obtained in good yields and the functional group tolerance of the process was excellent (Scheme 3. . In 2018, Wang [44] and Shen [33], concomitantly reported the use of the above-mentioned reagent 7 to get access to monofluoromethylthioesters, starting from aldehydes. While Wang was using AMBN (2,2′-Azobis(2-methylbutyronitrile)) to promote the acyl radical formation followed by its recombination with SCH2F moiety onto a broad range of aldehydes, Shen used the combination of NaN3 and PIFA to carry out the same transformation.…”

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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“…Then acyl radical A reacts with PhSO 2 SCF 2 H to afford the target product 48 and PhSO 2 radical (Scheme 22). Subsequently, the same authors extended this methodology for the synthesis of monofluoromethylthioesters [63]. They found that the reaction of same set of aldehydes 47 with PhSO 2 SCH 2 F employing 2,2'-azobisisovaleronitrile (AMBN) as the radical initiator in refluxing DCE, afforded the corresponding monofluoromethylthioesters with yield range from 42% to 91%.…”

Section: Fluoroalkylation Of Aldehydes With Arso 2 Sr F Reagentsmentioning

confidence: 99%

Methods for the direct synthesis of thioesters from aldehydes: a focus review

Jabarullah

Jermsittiparsert

Melnikov

et al. 2019

Journal of Sulfur Chemistry

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Direct C-H bond functionalization chemistry allows the pot-, atom-, and step-economical and original construction of carbon-carbon and carbon-heteroatom bonds starting from hydrocarbons (or hydrocarbon fragments) without requiring pre-functionalization of the starting materials. In this context, synthesis of biologically and synthetically important thioesters through direct thioesterification of aldehydes has recently attracted considerable attention from organic synthetic communities, because aldehydes are cheap and widely abundant chemical materials. This review highlights up-todate developments and accomplishments in this interesting research arena with special emphasis on the mechanistic aspects of the reactions.

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Synthesis of Monofluoromethylthioesters from Aldehydes

Cited by 28 publications

References 68 publications

Exploration of new reaction tools for late-stage functionalization of complex chemicals

Exploration of new reaction tools for late-stage functionalization of complex chemicals

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

Methods for the direct synthesis of thioesters from aldehydes: a focus review

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Synthesis of Monofluoromethylthioesters from Aldehydes

Cited by 28 publications

References 68 publications

Exploration of new reaction tools for late-stage functionalization of complex chemicals

Exploration of new reaction tools for late-stage functionalization of complex chemicals

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

Methods for the direct synthesis of thioesters from aldehydes: a focus review

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