Remote trifluoromethylthiolation of alcohols under visible light

Barday, Manuel; Blieck, Rémi; Ruyet, Louise; Besset, Tatiana

doi:10.1016/j.tet.2020.131153

Cited by 15 publications

(14 citation statements)

References 106 publications

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“…More recently, Besset and coworkers were able to functionalize aliphatic alcohols in the presence of a hypervalent iodine as oxidant under blue light irradiation (Scheme 10, right). [34] Keeping in mind the volatility of the formed products 32, the yields remained moderate. Moreover, it appears that the reaction is sensitive to steric hindrance when secondary or tertiary alcohols were evaluated.…”

Section: S-(fluoroalkyl) Thiosulfonatesmentioning

confidence: 98%

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Ghiazza

Billard

2021

Eur J Org Chem

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Reagent design is at the cornerstone of modern organofluorine chemistry. The past decades have seen the emergence of diverse families of reagents with the aim of introducing fluoroalkylthio or seleno groups in an efficient and selective way. Among them, highly versatile fluoroalkyl thiosulfonates and selenosulfonates are in the foreground of the recent developments. Their applicability is discussed in detail in this Minireview, with a specific focus on the reactivity and activation modes.

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Section: S-(fluoroalkyl) Thiosulfonatesmentioning

confidence: 98%

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Ghiazza

Billard

2021

Eur J Org Chem

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“…After reaction between the radical B and the complex III, the intermediate IV would be obtained and this latter would undergo a reductive elimination to afford the desired products 33 or 35 and regenerate the active Cu (I) catalyst. More recently, Besset and co-workers [30] reported, for the first time, a selective remote -trifluoromethylthiolation of aliphatic alcohols [31] mediated by an alkoxy radical. In the presence of (diacetoxyiodo)benzene (PIDA) and the TolSO2SCF3 reagent, a two-step process (trifluoromethylthiolation/acetoxylation) was developed under blue light irradiation affording the desired products with a full -selectivity (Scheme 13, 16 examples, up to 51% yield).…”

Section: Trifluoromethylthiolation and Trifluoromethylselenation Reactionsmentioning

confidence: 99%

“…More recently, Besset and co‐workers [30] reported, for the first time, a selective remote δ‐trifluoromethylthiolation of aliphatic alcohols [6c, 31] mediated by an alkoxy radical. In the presence of (diacetoxyiodo)benzene (PIDA) and the TolSO 2 SCF 3 reagent, a two‐step process (trifluoromethylthiolation/acetoxylation) was developed under blue light irradiation affording the desired products with full δ‐selectivity (Scheme 13, 16 examples, up to 51 % yield).…”

Section: Distal Functionalization Via 15‐hydrogen Atom Transfermentioning

confidence: 99%

Radical‐Promoted Distal C−H Functionalization of C(sp³) Centers with Fluorinated Moieties

2021

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Due to their unique properties, fluorinated scaffolds are pivotal compounds in pharmaceuticals, agrochemicals and materials science. Over the last years, the development of versatile strategies for the selective synthesis of fluorinated molecules by direct C−H bond functionalization has attracted a lot of attention. In particular, the design of novel transformations based on a radical process was a bottleneck for the distal C−H functionalization reactions, offering synthetic solutions for the selective introduction of a fluorinated group. This Minireview highlights the major contributions that have been made in this blossoming field. The development of new methodologies for the remote functionalization of aliphatic derivatives with various fluorinated groups based on a 1,5-HAT process and a -fragmentation reaction will be mainly showcased and discussed.Scheme 3. Synthesis of -fluorinated ketone derivatives via an iminyl radical generated by a photoredox process. Acr + -Mes ClO4 -= 9-mesityl-10methylacridinium perchlorate. Boc = tert-butyloxycarbonyl.Aiming at developing a general approach, the same group showed that changing the nature of the nitrogen radical, from iminyl radicals to amidyl ones, the fluorination of remote tertiary, secondary and primary C−H bonds was possible (Scheme 4, 31 examples, up to 89% yield). [11] Using an Ir (III) catalyst, in the presence of Selectfluor along with cesium carbonate, an access to fluorinated amide derivatives at the -position was developed starting from the corresponding carboxylic acid precursors 3. The reaction proved to be efficient for the remote fluorination of tertiary (3a), secondary (3b), and primary (3c) C(sp 3 ) centers leading to the corresponding fluorinated N-methyl amides (4a-c). Note that the fluorination of a benzylic position was possible and the compound 4d was synthesized in a good yield. The transformation was not limited to the functionalization of N-methyl amides as the -fluorinated N-benzyl amide (4e) or the primary amide (4f) were successfully obtained. This distal fluorination was efficient on amides containing cycloalkyls (3g-i), offering an access to potentially interesting bioactive building blocks such as a N-Boc-piperidine (4i). The methodology was extended to the selective latestage remote fluorination of protected-amino acid derivatives (3j and 3k) and the dipeptide building block 3l. Furthermore, the transformation was not restricted to amide derivatives as the synthesis of fluorinated carbamate (4m) and N-protected amines (4n-p) at the -and -positions, respectively, was also possible. When the amide (3q) or the carbamate (3r) bearing a competitive tertiary center at the -position was used, the fluorination at this position was preferentially achieved via a 1,6-HAT process. [12] However, in case of the N-Boc-protected amine 3s, a mixture of fluorinated products (4s and 4s') at the -and -positions was obtained in a 1:1 ratio, presumably due to a higher chain flexibility. The following mechanism was suggested: under basic conditi...

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“… Trifluoromethylthiolation of free alcohols under visible light [30] . [a] 1.2 equiv.…”

Section: Distal Functionalization Via 15‐hydrogen Atom Transfermentioning

confidence: 99%

Radical‐Promoted Distal C−H Functionalization of C(sp³) Centers with Fluorinated Moieties

2021

Self Cite

View full text Add to dashboard Cite

Due to their unique properties, fluorinated scaffolds are pivotal compounds in pharmaceuticals, agrochemicals, and materials science. Over the last years, the development of versatile strategies for the selective synthesis of fluorinated molecules by direct C−H bond functionalization has attracted a lot of attention. In particular, the design of novel transformations based on a radical process was a bottleneck for distal C−H functionalization reactions, offering synthetic solutions for the selective introduction of fluorinated groups. This Minireview highlights the major contributions in this blossoming field. The development of new methodologies for the remote functionalization of aliphatic derivatives with various fluorinated groups based on a 1,5‐hydrogen atom transfer process and a β‐fragmentation reaction will be showcased and discussed.

show abstract

Remote trifluoromethylthiolation of alcohols under visible light

Cited by 15 publications

References 106 publications

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Radical‐Promoted Distal C−H Functionalization of C(sp³) Centers with Fluorinated Moieties

Radical‐Promoted Distal C−H Functionalization of C(sp³) Centers with Fluorinated Moieties

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Remote trifluoromethylthiolation of alcohols under visible light

Cited by 15 publications

References 106 publications

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Synthesis, Reactivity and Activation Modes of Fluoroalkyl Thiosulfonates and Selenosulfonates

Radical‐Promoted Distal C−H Functionalization of C(sp3) Centers with Fluorinated Moieties

Radical‐Promoted Distal C−H Functionalization of C(sp3) Centers with Fluorinated Moieties

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Product

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About

Radical‐Promoted Distal C−H Functionalization of C(sp³) Centers with Fluorinated Moieties

Radical‐Promoted Distal C−H Functionalization of C(sp³) Centers with Fluorinated Moieties