Photocatalytic C–F alkylation; facile access to multifluorinated arenes

Singh, Anuradha; Kubik, Jonathan; Weaver, Jimmie D.

doi:10.1039/c5sc03013g

Cited by 124 publications

(72 citation statements)

References 60 publications

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“…7, 9, 12 Although many of the spectra match experiment, two of the structures had large errors (Chart 3, red). Based on the correction described above, revised structures were tested and these match the experimental values within the error expected for our scaling factors.…”

Section: Resultsmentioning

confidence: 99%

Prediction of ¹⁹F NMR Chemical Shifts for Fluorinated Aromatic Compounds

et al. 2018

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Scaling factors are reported for use in predicting 19F NMR chemical shifts for fluorinated (hetero)aromatic compounds with relatively low levels of theory. Our recommended scaling factors were developed using a curated data set of >50 compounds, with 100 individual 19F shifts spanning a range of >150 ppm. With a maximum deviation of 6.5 ppm between experimental and computed shifts, or 4% of the range tested, these scaling factors allow for the assignment of chemical shifts to specific fluorines in multifluorinated aromatics. The utility of this approach is highlighted by several structural reassignments.

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Section: Resultsmentioning

confidence: 99%

Prediction of ¹⁹F NMR Chemical Shifts for Fluorinated Aromatic Compounds

et al. 2018

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“…Our group 1,39 has routinely used 3 in our standard catalyst screen, and likewise Ooi and coworkers 40 synthesized this catalyst in their asymmetric α-coupling of N -arylaminomethanes and used the photocatalyst in their optimization experiments. 3 is thus included in order to provide electrochemical and photophysical data.…”

Section: Photocatalyst Detailsmentioning

confidence: 99%

“…1–4 Historically these complexes have been primarily employed in solar cells, 5 light emitting diodes (LEDs), 6 and as initiators in free radical polymerizations. 7 Both of the prototypical complexes, Ru(bpy) 32+ and Ir(ppy) 3 are d 6 , coordinatively saturated, 18-electron complexes.…”

Section: Introductionmentioning

confidence: 99%

Advances in Photocatalysis: A Microreview of Visible Light Mediated Ruthenium and Iridium Catalyzed Organic Transformations

Day

Teegardin

Weaver

et al. 2016

Org. Process Res. Dev.

396

329

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“…Returning to the problem of multifluorinated arenes, we have previously demonstrated that the perfluoroaryl radical is a powerful intermediate for the functionalization of perfluoroarenes, which can elicit C–F alkylation, 16 arylation, 17 and alkenylation. 18 While the perfluoroaryl radical has proven competent for cross-coupling, the inherent limitation is the regioselectivity of the C–F fragmentation event.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bond Directed Photocatalytic Hydrodefluorination: Overcoming Electronic Control

2017

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The photocatalytic C–F functionalization of highly fluorinated arenes is a powerful method for accessing functionalized multifluorinated arenes. The decisive step in the determining regioselectivity in fluorine functionalization is fluoride fragmentation from the radical anion of the multifluorinated arene. To date, the availability of regioisomers has been dictated by the innate electronics of the fluorinated arene, limiting the synthetic utility of the chemistry. This study investigates the remarkable ability of a strategically located hydrogen bond to transcend the normal regioselectivity of the C–F functionalization event. A significant rate acceleration is additionally observed for hydrodefluorination of fluorines that can undergo intramolecular hydrogen bonds that form 5–8 membered cycles with moderately acidic N–Hs. The hydrogen bond is expected to facilitate the fragmentation not only by bending the C–F bond of the radical anion out of planarity, but also by increasing the exothermicity of the fluoride extrusion step through protonation of the naked fluoride. Finally, the synthetic utility of the method is demonstrated in an expedited synthesis of the trifluorinated α-phenyl acetic acid derivative required for the commercial synthesis of Januvia, an anti-diabetic drug. This represents the first synthesis of a commercially important multifluorinated arene via a defluorination strategy, and is significantly shorter than the current strategy.

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Photocatalytic C–F alkylation; facile access to multifluorinated arenes

Abstract: From the top down; access to complex multifluorinated arenes via multiple photocatalytic C–F substitutions.

Cited by 124 publications

References 60 publications

Prediction of ¹⁹F NMR Chemical Shifts for Fluorinated Aromatic Compounds

Prediction of ¹⁹F NMR Chemical Shifts for Fluorinated Aromatic Compounds

Advances in Photocatalysis: A Microreview of Visible Light Mediated Ruthenium and Iridium Catalyzed Organic Transformations

Hydrogen Bond Directed Photocatalytic Hydrodefluorination: Overcoming Electronic Control

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Photocatalytic C–F alkylation; facile access to multifluorinated arenes

Abstract: From the top down; access to complex multifluorinated arenes via multiple photocatalytic C–F substitutions.

Cited by 124 publications

References 60 publications

Prediction of 19F NMR Chemical Shifts for Fluorinated Aromatic Compounds

Prediction of 19F NMR Chemical Shifts for Fluorinated Aromatic Compounds

Advances in Photocatalysis: A Microreview of Visible Light Mediated Ruthenium and Iridium Catalyzed Organic Transformations

Hydrogen Bond Directed Photocatalytic Hydrodefluorination: Overcoming Electronic Control

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Prediction of ¹⁹F NMR Chemical Shifts for Fluorinated Aromatic Compounds

Prediction of ¹⁹F NMR Chemical Shifts for Fluorinated Aromatic Compounds