Photochemical oxyfluoroalkylation of styrenes by the addition of perfluoroalkyl radicals in an atmosphere of oxygen

Visible-Light-Promoted Hydroxydifluoroalkylation of Alkenes Enabled by Electron Donor–Acceptor Complex

“…On the basis of our control experiments and previous reports, , a tentative EDA-enabled mechanism for this transformation is proposed in Scheme c. The reaction was initiated by photoexcitation of the EDA complex I or II .…”

Universal Group 14 Free Radical Photoinitiators for Vinylidene Fluoride, Styrene, Methyl Methacrylate, Vinyl Acetate, and Butadiene

“…Besides Bu 3 SnH being a great hydride donor, − which reduces semi/perfluorinated chlorides and iodides, Bu 3 Sn • is a much more efficient halide activator than Mn 2 (CO) 10 ( k Bu3Sn / k Mn(CO)5 > 10 4 vs PhCH 2 Br), , which easily ,, abstracts halides (Cl/Br/I, k abstr ∼ 10 2–6 /10 6–9 /10 9 M –1 s –1 ) and pseudohalides (PhS– 10 5 M –1 s –1 ; PhGe–, 10 8 M –1 s –1 ) from alkyl , or Br and I from aryl − or vinyl derivatives ( k abstr ∼ 10 6–7 M –1 s –1 ). Alkyl fluorides or perfluorinated substrates remain inert, , but alkyl halides, especially iodides and (fluoro)­alkyl iodides, − are radically activated. Me 6 Sn 2 reacts with CF 3 I under UV and similarly to Bu 6 Sn 2 catalyzes radical additions of various R F –I.…”

“…Alkyl fluorides or perfluorinated substrates remain inert, , but alkyl halides, especially iodides and (fluoro)­alkyl iodides, − are radically activated. Me 6 Sn 2 reacts with CF 3 I under UV and similarly to Bu 6 Sn 2 catalyzes radical additions of various R F –I. Like Mn­(CO) 5 X, Bu 3 SnX derivatives (X = Cl, Br, I) are too stable (BDE Bu 3 Sn–I = 77 kcal/mol) and inert, as reversible radical halides transfer agents toward a growing polymer radical.…”

Redox system for perfluoroalkylation of arenes and α-methylstyrene derivatives using titanium oxide as photocatalyst

“…However, in the reaction with a-methylstyrene, the produced benzyl-type radical is very stable against iodine abstraction from the perfluoroalkyl iodide and the iodoperfluoroalkylation does not proceed (Scheme 5) [13,20,21]. We have been investigating ways for the produced benzyl-type radical to undergo further reaction for the preparation of fluoroalkylated compounds [13,21], and found a new way to convert the radical to a cation (Scheme 6).…”

“…We have been investigating ways for the produced benzyl-type radical to undergo further reaction for the preparation of fluoroalkylated compounds [13,21], and found a new way to convert the radical to a cation (Scheme 6). The system consists of three steps: one-electron reduction of perfluoroalkyl iodide, the addition of the radical to the olefin and one-electron oxidation of the produced benzyl-type radical to the cation.…”