Visible-light-induced thiotrifluoromethylation of terminal alkenes with sodium triflinate and benzenesulfonothioates

Kong, Weiguang; An, Hejun; Song, Qiuling

doi:10.1039/c7cc03520a

Cited by 68 publications

(24 citation statements)

References 77 publications

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“…Thiotrifluoromethylation of terminal alkenes is another interesting example of photoreduction using CF 3 SO 2 Na as the CF 3 radical source and benzenesulfonothioates as the sulfur source (Scheme ). Traditional reports of C–CF 3 bond synthesis follows oxidative quenching but this protocol follows an unconventional reductive quenching pathway as revealed by the mechanistic studies.…”

Section: Discussionmentioning

confidence: 99%

Alternate Energy Sources for Sustainable Organic Synthesis

Mandal¹

2019

ChemistrySelect

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Organic Chemistry plays an important role in energy, information, materials, population, health, environment and implementation of defence plan. Organic chemists therefore, have the greatest responsibility to devise methods of carrying out organic syntheses, which will reduce or even eliminate the byproducts and solve the problem of environmental pollution from the source. One of the methods to achieve this is using non-conventional energy sources, such as microwave, ultrasound, and photochemical chemistry, in conjugation with nontoxic solvents, which dramatically reduces energy waste and reaction time. Experiments synergising these alternate energy sources like microwave sonication, photosonication or microwave photochemistry, have gained high popularity as costeffective green strategies. Pooling the advantages of alternate energy sources with biocatalysis is another novel avenue of sustainable synthesis. Organic electrosynthesis has also emerged as an environmentally benign technique for the construction of C-C and C-hetero bonds. Highlights of significant developments in these areas define the scope of the present discussion.

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Section: Discussionmentioning

confidence: 99%

Alternate Energy Sources for Sustainable Organic Synthesis

Mandal¹

2019

ChemistrySelect

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“…Song et al. employed benzenethiosulfonates ( 7 ) as a sulfenyl source and sodium triflinate ( 313 ) (Langlois reactant) as an easily‐handled CF 3 ( 316 ) radical source (Scheme , route 1), obtained via involvement of a photoredox catalyst, in a three‐component reaction with unactivated alkene ( 240 ) . The reaction is believed to go via a reductive quenching cycle, generating an anion intermediate 318 , formed from 317 by accepting an electron from the photoredox catalyst.…”

Section: Applications Of Thiosulfonates In Synthesismentioning

confidence: 99%

Thiosulfonates as Emerging Reactants: Synthesis and Applications

et al. 2019

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The synthetic strategies towards thiosulfonates (RSO2SR1) are comprehensively reviewed from their original discovery to recent advances. Incorporation of the green credentials of the synthetic procedures towards thiosulfonates allows one to judge the merits of the state of the art, beyond the typical yield of a product and availability of the reactants. As reactant for organic transformations, thiosulfonates are particularly interesting given their possibility to react with nucleophiles, electrophiles and radicals. This review aims to give researchers, not familiar with the field, a good understanding of the general applications of thiosulfonates, while not skipping the recent important advances. The related, but less explored, selenosulfonates (RSO2SeR1) are also covered.

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“…Further, also simple alkenes could be used as radical traps involving aliphatic carbon nucleophiles. 16 Several impressive variants of this strategy have since then been developed, mostly using CO 2 as the electrophile. 17 Examples comprise the use of H–P(O)R 2 phosphonyl compounds 17a and simple silanes 17b as radical precursor to achieve the corresponding alkene difunctionlization.…”

Section: Carbanion Generation Via Radical Reductionmentioning

confidence: 99%

“…In terms of intermolecular reactions, the concept of photocatalytic radical reduction was up to this point only reported for CO 2 (vide supra), aromatic aldehydes, 31 benzenesulfonothioates, 16 and highly electron-deficient Michael acceptors 32 as electrophiles.…”

Section: Carbanion Generation Via Radical Reductionmentioning

confidence: 99%

Strategies for the Photocatalytic Generation of Carbanion Equivalents for Reductant-Free C–C Bond Formations

Donabauer

König

2020

Acc. Chem. Res.

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Conspectus The use of photocatalysis in organic chemistry has encountered a surge of novel transformations since the start of the 21st century. The majority of these transformations are driven by the generation and subsequent reaction of radicals, owing to the intrinsic property of common photocatalysts to transfer single electrons from their excited state. While this is a powerful and elegant method to develop novel transformations, several research groups recently sought to further extend the toolbox of photocatalysis into the realm of polar ionic reactivity by the formation of cationic as well as anionic key reaction intermediates to furnish a desired product. Our group became especially interested in the photocatalytic formation of anionic carbon nucleophiles, as the overall transformation resembles classical organometallic reactions like Grignard, Barbier, and Reformatsky reactions, which are ubiquitous in organic synthesis with broad applications especially in the formation of valuable C–C bonds. Although these classical reactions are frequently applied, their use still bears certain disadvantages; one is the necessity of an (over)stoichiometric amount of a reducing metal. The reducing, low-valent, metal is solely applied to activate the starting material to form the organometallic carbanion synthon, while the final reaction product does generally not contain a metal species. Hence, a stoichiometric amount of metal salt is bound to be generated at the end of each reaction, diminishing the atom economy. The use of visible light as mild and traceless activation agent to drive chemical reactions can be a means to arrive at a more atom economic transformation, as a reducing metal source is avoided. Beyond this, the vast pool of photocatalytic activation methods offers the potential to employ easily available starting materials, as simple as unfunctionalized alkanes, to open novel and more facile retrosynthetic pathways. However, as mentioned above, photocatalysis is dominated by open-shell radical reactivity. With neutral radicals showing an intrinsically different reactivity than ionic species, novel strategies to form intermediates expressing a polar behavior need to be developed in order to achieve this goal. In the last couple of years, several methods toward this aim have been reported by our group and others. This Account aims to give an overview of the different existing strategies to photocatalytically form carbon centered anions or equivalents of those in order to form C–C bonds. As the main concept is to omit a stoichiometric reductant source (like a low-valent metal in classical organometallic reactions), only redox-neutral and reductant-free transformations were taken into closer consideration. We present selected examples of important strategies and try to illustrate the intentions and concepts behind the methods developed by our group and others.

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Visible-light-induced thiotrifluoromethylation of terminal alkenes with sodium triflinate and benzenesulfonothioates

Cited by 68 publications

References 77 publications

Alternate Energy Sources for Sustainable Organic Synthesis

Alternate Energy Sources for Sustainable Organic Synthesis

Thiosulfonates as Emerging Reactants: Synthesis and Applications

Strategies for the Photocatalytic Generation of Carbanion Equivalents for Reductant-Free C–C Bond Formations

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