Synthesis of Trifluoromethylated Dithiocarbamates via Photocatalyzed Substitution Reaction: Pentafluoropyridine as Activating Reagent

Zemtsov, Artem A.; Lunkov, Sergey S.; Levin, Vitalij V.; Dilman, Alexander D.

doi:10.1002/ejoc.202001572

“…Similarly, same signature was observed with PBN where corresponding adduct G (PBN-A adduct, g=2.006, aN=14.8G aH=2.2G, present in 40%) was observed in conjunction with that of the previously characterized E (Figure 2, g). 24 Considering the obtained results, we were able to propose the following mechanisms. Regarding the synthesis of fluorinated hexestrol derivatives, SET oxidation of the Langlois reagent by PC1 at its excited state allow the formation of CF3 radical.…”

Section: Resultsmentioning

confidence: 85%

Tailoring the Reactivity of the Langlois Reagent and Styrenes with Cyanoarenes Organophotocatalysts under Visible-Light.

Louvel

¹

,

Souibgui

²

,

Taponard

³

et al. 2021

Preprint

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The unprecedented selective and straightforward one-step access to fluoroalkylated hexestrol derivatives, nonsteroidal estrogens, is achieved in good to excellent isolated yields under organophotoredox conditions by using the stable and easy to handle Langlois reagent. Furthermore, the challenging selective hydrotrifluoromethylation of styrenes proceeds under mild reaction conditions without the requirement of any additive. We assume that the solvent drives the reaction pathway towards either the reduction or the dimerization of the radical intermediate generated after initial addition of the fluoroalkyl radical to the styrene. The versatility of the developed system is also extended to encompass radical-radical cross-coupling as exemplified here using cyanopyridine. Mechanistic investigations including luminescence and EPR spectroscopy allow to shed the light on the different mechanisms.

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“…Similarly, the same signature was observed with PBN where the corresponding adduct G (PBN-A adduct, g = 2.006, a N = 14.8G a H = 2.2G, present in 40%) was observed in the presence of the previously characterized E (Figure 2g). [27] The aforementioned results allowed us to propose the following mechanisms. Regarding the synthesis of fluorinated hexestrol derivatives, SET oxidation of the Langlois reagent by the excited PC1 allows the formation of CF 3 radical.…”

Section: Resultsmentioning

confidence: 92%

Tailoring the Reactivity of the Langlois Reagent and Styrenes with Cyanoarenes Organophotocatalysts under Visible‐Light

Louvel

¹

,

Souibgui

²

,

Taponard

³

et al. 2021

View full text Add to dashboard Cite

The selective one-step access to fluoroalkylated hexestrol derivatives, nonsteroidal estrogens, is achieved in good to excellent isolated yields under organophotoredox conditions by using the stable and easy to handle Langlois reagent.Furthermore, the challenging selective hydrotrifluoromethylation of styrenes proceeds under mild reaction conditions without the requirement for any additive. We assume that the solvent drives the reaction pathway towards either the reduction or the dimerization of the radical intermediate generated after initial addition of the fluoroalkyl radical to the styrene. The versatility of the developed system is also extended to encompass radical-radical cross-coupling as exemplified here using cyanopyridine. Mechanistic investigations including luminescence and EPR spectroscopy allow to shed the light on the different mechanisms.

show abstract

“…Similarly, the same signature was observed with PBN where the corresponding adduct G (PBN-A adduct, g=2.006, aN=14.8G aH=2.2G, present in 40%) was observed in the presence of the previously characterized E (Figure 2, g). [27] The aforementioned results allowed us to propose the following mechanisms. Regarding the synthesis of fluorinated hexestrol derivatives, SET oxidation of the Langlois reagent by the excited PC1 allow the formation of CF3 radical.…”

Section: Resultsmentioning

confidence: 92%

Tailoring the Reactivity of the Langlois Reagent and Styrenes with Cyanoarenes Organophotocatalysts under Visible-Light.

Louvel

¹

,

Souibgui

²

,

Taponard

³

et al. 2021

Preprint

1

0

View full text Add to dashboard Cite

The unprecedented selective and straightforward one-step access to fluoroalkylated hexestrol derivatives, nonsteroidal estrogens, is achieved in good to excellent isolated yields under organophotoredox conditions by using the stable and easy to handle Langlois reagent. Furthermore, the challenging selective hydrotrifluoromethylation of styrenes proceeds under mild reaction conditions without the requirement of any additive. We assume that the solvent drives the reaction pathway towards either the reduction or the dimerization of the radical intermediate generated after initial addition of the fluoroalkyl radical to the styrene. The versatility of the developed system is also extended to encompass radical-radical cross-coupling as exemplified here using cyanopyridine. Mechanistic investigations including luminescence and EPR spectroscopy allow to shed the light on the different mechanisms.

show abstract

Synthesis of Trifluoromethylated Dithiocarbamates via Photocatalyzed Substitution Reaction: Pentafluoropyridine as Activating Reagent

Cited by 11 publications

References 36 publications

Tailoring the Reactivity of the Langlois Reagent and Styrenes with Cyanoarenes Organophotocatalysts under Visible-Light.

Tailoring the Reactivity of the Langlois Reagent and Styrenes with Cyanoarenes Organophotocatalysts under Visible-Light.

Tailoring the Reactivity of the Langlois Reagent and Styrenes with Cyanoarenes Organophotocatalysts under Visible‐Light

Tailoring the Reactivity of the Langlois Reagent and Styrenes with Cyanoarenes Organophotocatalysts under Visible-Light.

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