Cation-π-interaction-facilitated, self-photocatalyzed and regioselective perfluoroalkylation of 3-aza-1,5-dienes

Electrophotocatalysis Versus Indirect Electrolysis: Electrochemical Selenocyclization of 3‐Aza‐1,5‐dienes Facilitated by Energy Transfer, Direct Photolysis or N‐Hydroxyphthalimide

“…While diselenide 2 a absorbs the visible‐light photons efficiently, both substrate 1 a and product 3 a marginally absorb light above 395 nm. All three might act as photosensitizers, and both 3‐aza‐1,5‐dienes and 4‐pyrrolin‐2‐ones have been reported to be photoreductants in the presence of a photoactivator [26c] . Stern‐Volmer studies showed that diselenide 2 a could quench the excited‐states of both 1 a and 3 a as well (Figures S44 and S45), and the estimated excited‐state reduction potentials of 1 a (2.79 V vs .…”

“…Ag/AgCl, see the Supporting Information) are high enough to allow the oxidation of 2 a . Be that as it may, attempts to use 1 a or 3 a as a photooxidant under violet‐light irradiation in some established redox‐neutral reactions with a reductive quenching photocatalytic cycle met with no success (Schemes 7c and S1‐S6), probably due to their poor absorptions at 395 nm without a photoactivator, [26c] and a light source with a shorter wavelength might be required (Scheme S7). On the other hand, although the calculated triplet energies of 1 a (50.6 kcal mol −1 ) and 3 a (54.0 kcal mol −1 ) far exceed that of 2 a (Scheme 7d and Table S20), [46] under violet‐light irradiation 1 a and 3 a also failed to act as an EnT PC in a typical EnT reaction of chalcone dimerization (Schemes 7e and S8), probably also due to the mismatched irradiation wavelength.…”

“…The authors have cited additional references within the Supporting Information [9b,26c,f,g,44,46,49–54] …”

Electrochemical Sulfonylation/Cyclization of N-Alkenylacrylamides with Sodium Sulfinates or Sulfonyl Hydrazides

“…4-Pyrrolin-2-ones are core structural elements in both natural alkaloids and synthetic compounds . We, ,,, along with other researchers, , have successfully synthesized a variety of 4-pyrrolin-2-ones with specific groups through the cyclization reaction of N -alkenylacrylamides. However, most of these methods still require reaction conditions that are not in line with green chemistry principles, such as high temperatures or the use of precious metals.…”