Visible-light Promoted Atom Transfer Radical Addition−Elimination (ATRE) Reaction for the Synthesis of Fluoroalkylated Alkenes Using DMA as Electron-donor

Xu, Wenwen; Wang, Le; Mao, Ting; Gu, Jiwei; Li, Xiaofei; He, Chun‐Yang

doi:10.3390/molecules25030508

Cited by 11 publications

(9 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2020, He and co-workers reported photoinduced transition-metal-free ATRE perfluoroalkylation of allenes. 58 Mechanistically, the photosensitive activity of the EDA complex from the solvent DMA (as the electron donor) and perfluoroalkyl iodide plays a key role for the generation of Scheme 25 Photoinduced, halogen bond promoted double radical isocyanide insertion with perfluoroalkyl iodides…”

Section: Scheme 28 Photoinduced Eosin Y Catalyzed Atre Reaction Of Al...mentioning

confidence: 99%

Recent Advances in Photoinduced Perfluoroalkylation Using Perfluoroalkyl Halides as the Radical Precursors

Tang¹,

Liu²,

Liu³

et al. 2022

Synthesis

View full text Add to dashboard Cite

Perfluoroalkylation is one of the most important methods for the introduction of multiple fluorine atoms into organic molecules in a single step. The use of photoinduced technology is a common strategy that uses the outstanding oxidation or reduction ability of a photoredox catalyst in its excited state to generate perfluoroalkyl radicals from perfluoroalkyl halides. The perfluoroalkyl radicals thus obtained can undergo various subsequent reactions under mild conditions, such as ATRA reaction of alkenes, alkynes, and 1,n-enynes; carbo/heteroperfluoroalkylation of alkenes and isocyanides; and C–H/F perfluoroalkylation. This allows the expedient incorporation of various perfluoroalkyl groups into the molecular motifs. Perfluorinated functional groups are still in demand in pharmaceutical and material sciences; this short review discusses recent advances in photoinduced perfluoroalkylation methodologies and technologies.1 Introduction2 Photocatalytic Perfluoroalkylation of Alkenes, Alkynes, and 1,n- Enynes3 Photocatalytic Carboperfluoroalkylation or Heteroperfluoroalkylation of Alkenes, Alkynes, Isocyanides, and Hydrazones4 Photocatalytic ATRE Reactions of Alkenes with Perfluoroalkyl Halides5 Photocatalytic C–X (X = H, F) Bond Perfluoroalkylation6 Continuous Flow Strategies in Photocatalytic Perfluoroalkylation7 Conclusions

show abstract

Section: Scheme 28 Photoinduced Eosin Y Catalyzed Atre Reaction Of Al...mentioning

confidence: 99%

Recent Advances in Photoinduced Perfluoroalkylation Using Perfluoroalkyl Halides as the Radical Precursors

Tang¹,

Liu²,

Liu³

et al. 2022

Synthesis

View full text Add to dashboard Cite

show abstract

“…Photocatalyzed atom transfer radical additions (PhATRAs) to olefins have been found with metal photocatalysts, such as the polypyridyl complexes of Ir- , and Ru-based photocatalysts, − Bi 2 O 3 , , Cu-derived complexes activated by light, − TiO 2 , and Au complexes in organic solvents. Nonmetal–organic photocatalysts, such as 4-methoxybenzaldehyde, , and light-activated halogen-bonding complexes , have also been reported to perform ATRA reactions. Pyrene-based metal organic frameworks have been found to achieve ATRA products .…”

Section: Radical Additions To Carbon–carbon Multiple Bonds In Aqueous...mentioning

confidence: 99%

Advances in Photocatalytic Organic Synthetic Transformations in Water and Aqueous Media

Barata‐Vallejo

Yerien

Postigo

2021

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Advances in visible light-photocatalyzed preparative synthetic organic transformations in water or aqueous media are studied. Both the convenience of visible light photocatalytic strategies to achieve synthetic organic transformations and the employment of water or aqueous mixtures make this approach a very resourceful methodology. Mechanistic aspects for such photocatalyzed processes are discussed. The effects of water in the stereoselectivity of some reactions and considerations regarding the improved enantioselectivity in chiral catalytic photoredox reactions are manifested with the use of water. The use of water as a result of a protocol improvement or environmentally friendlier methodology as compared to the same reaction performed in organic solvents are also considered. All these combined effects of water as a reaction medium or its very presence in photocatalytic reactions have an ultimate goal which is to diminish the environmental impact of synthetic and photocatalytic processes. This perspective highlights the progress and state of the art organic transformations realized by photocatalytic techniques in water or aqueous systems as well as water as a reactant. In this regard, aromatic substitution reactions, radical additions to carbon–carbon double bonds, photooxidation reactions, decarboxylation processes, and miscellaneous reactions are presented.

show abstract

“…For comparison, calculations were carried out on a series of weaker nitrogen Lewis bases such as pyridine or aniline, but also oxygen in Lewis bases such as propylene oxide (PO), THF, acetone and dimethylacetamide (DMA), the latter two being used recently for the activation of perfluoroalkylation reactions. [10,11] The energy minimized structures of the conformers for the [C 4 F 9 I-acetone] and [C 4 F 9 I-DMA] complexes are depicted in Figure 8. LB] complexes calculated at the M06-2X level of theory using the DGDZVP basis set.…”

Section: Structural and Energetic Considerationsmentioning

confidence: 99%

“…In this context, the case of radical perfluoroalkylation reactions is of particular interest. While numerous visible light-promoted perfluoroalkylations involve halogen bonding interactions between Rf-I and a variety of Lewis bases having lone pairs of electrons centered on oxygen, [10,11] nitrogen, [12][13][14][15][16] or phosphorus [17,18]) atoms, a detailed understanding of the mechanism at work in these photochemical processes is still required. Characterization of the postulated EDA complexes is typically conducted using UV-Visible spectroscopy in order to identify a possible bathochromic shift and/or the appearance of a new electronic absorption band.…”

Section: Introductionmentioning

confidence: 99%

“…The latter two being used recently for the activation of perfluoroalkylation reactions. [10,11] By combining this set of experimental and theoretical approaches, we determined the strength of the halogen bond interactions occurring between C 4 F 9 I and Lewis bases, and revealed how it affects the UV-Visible spectrum of the Rf-I for its possible activation by visible light to generate Rf radicals.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Visible-light induced photochemistry of Electron Donor-Acceptor Complexes in Perfluoroalkylation Reactions: Investigation of halogen bonding interactions through UV–Visible absorption and Raman spectroscopies combined with DFT calculations

Grondin

Aupetit

Vincent

et al. 2021

Journal of Molecular Liquids

View full text Add to dashboard Cite

Visible light promoted perfluoroalkylation reactions initiated via halogen bonding interactions between perfluoroalkyl iodides (Rf-I, Rf=C n F 2n+1 ) and Lewis bases have been recognized as a powerful tool in the field of radical synthetic chemistry. In order to provide some insights into the nature, strength and role in the activation process of halogen bonding interactions, we have performed a combined UV-Visible/Raman/DFT study on a model Rf-I (C 4 F 9 I) and a series of Lewis bases (LB) frequently used for the activation of perfluoroalkylation reactions, including DBU, MTBD, TMG, TMEDA and Et 3 N. Raman studies conducted in acetonitrile solutions show that the band at 279 cm −1 associated with the C−I stretching normal mode of C 4 F 9 I shifts about 20 cm −1 towards lower wavenumbers upon formation of the halogenbonded complexes. Additionally, the Raman study revealed that at concentrations typically used for perfluoroalkylation reactions, the [C 4 F 9 I-LB] complexes are the main species present in solution. UV-Vis spectroscopy revealed that complex formation is characterized by a strong increase in absorption from 225 -350 nm. The higher the basicity of the Lewis base, the higher the increase of the UV absorbance.

show abstract

Visible-light Promoted Atom Transfer Radical Addition−Elimination (ATRE) Reaction for the Synthesis of Fluoroalkylated Alkenes Using DMA as Electron-donor

Cited by 11 publications

References 55 publications

Recent Advances in Photoinduced Perfluoroalkylation Using Perfluoroalkyl Halides as the Radical Precursors

Recent Advances in Photoinduced Perfluoroalkylation Using Perfluoroalkyl Halides as the Radical Precursors

Advances in Photocatalytic Organic Synthetic Transformations in Water and Aqueous Media

Visible-light induced photochemistry of Electron Donor-Acceptor Complexes in Perfluoroalkylation Reactions: Investigation of halogen bonding interactions through UV–Visible absorption and Raman spectroscopies combined with DFT calculations

Contact Info

Product

Resources

About