Photoinitiated Three-Component α-Perfluoroalkyl-β-heteroarylation of Unactivated Alkenes via Electron Catalysis

Abstract

A visible-light-initiated α-perfluoroalkyl-β-heteroarylation of various alkenes with perfluoroalkyl iodides and quinoxalin-2(1H)-ones is presented. This three-component radical cascade reaction allows an efficient synthesis of a range of perfluoroalkyl containing quinoxalin-2(1H)-one derivatives in moderate to excellent yields under mild conditions. Reactions proceed via acidic aminyl radicals that are readily deprotonated to give the corresponding radical anions able to sustain the radical chain as single electron transfer reducing reagents. Hence, the overall cascade classifies as an electron-catalyzed process.

Recent Advances in Photocatalytic Functionalization of Quinoxalin‐2‐ones

“…Continuing to review the photoinduced alkylation methodologies of quinoxalin-2-ones, in 2019 Armido Studer reported an elegant approach through a catalyst-free tricomponent reaction. [41] Under the irradiation of Blue LEDs, they were capable of coupling quinoxalin-2-ones with alkenes and perfluoroalkyl iodides using DBU as base. Using these conditions, they could access a library of forty four C-3 alkylated-quinoxalin-2-ones, bearing multiple and complex substitution patterns in all involved reaction products, in good to excellent yields (Scheme 20).…”

Hypervalent Iodine(III)‐Promoted Rapid Cascade Reaction of Quinoxalinones with Unactivated Alkenes and TMSN3

“…HRMS (ESI): Calculated for C 16 154.87, 132.83, 132.61, 130.32, 129.80, 123.33, 114.07, 53.47, 48.04, 41.92, 36.52, 33.27, 30.86, 26.17, 25.79, 20.38, 14. 56,160.42,154.24,132.65,132.13,130.46,130.29,123.98,113.00,53.34,52.83,43.49,41.94,33.27,20.32,14.14. HRMS (ESI): Calculated for C 16 13 C NMR (126 MHz, CDCl 3 ) δ 166. 07,160.45,154.22,132.59,132.22,130.37,130.14,123.82,113.07,83.11,53.38,44.36,41.87,33.28,27.92,20.30,14.15.…”

“…78, 154.33, 137.37, 136.43, 133.18, 132.32, 130.95, 130.35, 130.23, 127.41, 126.75, 125.99, 123.73, 113.66, 53.86, 43.62, 29.14, 19.87 13 C NMR (126 MHz, CDCl 3 ) δ 157.87, 154. 16,135.90,134.86,133.31,132.25,130.52,130.47,130.21,128.72,128.37,126.84,123.81,113.73,52.91,44.53,29.17. HRMS (ESI): Calculated for C 17 58, 162.93, 159.86, 154.66, 153.27, 132.94, 132.46, 132.27, 130.32, 130.06, 123.79, 123.75, 122.95, 116.70, 115.70, 113.66, 90.37, 68.85, 53.52, 41.74, 30.32, 29.23, 28.42, 23.36 1-(2-Bromobenzyl)-3-(1-(4-phenyl-1H-1,2,3-triazol-1-yl) (d, J = 12.7 Hz, 1H), 5.51 (d,J = 12.8 Hz,1H),5.06 (dd,J = 13.6,8.8 Hz,1H),4.78 (dd,J = 13.6,5.6 Hz,1H),.07 (m, 1H), 2.00-1.91 (m, 1H), 1.72 (ddd, J = 9.9, 7.0, 4.6 Hz, 1H), 1.33 (ddd, J = 7.1, 3.9, 2.3 Hz, 2H), 0.85 (t, J = 7.3 Hz, 3H).…”

Iron(III)-Mediated Rapid Radical-Type Three-Component Deuteration of Quinoxalinones With Olefins and NaBD4

“…Multicomponent transformations were rarely reported. In 2019, Studer and coworkers demonstrated a visible-light-initiated three-component reaction of quinoxalinones, olefins, and perfluoroalkyl iodides (Zheng and Studer, 2019 ). In the same year, Koley's group disclosed a metal-free domino three-component radical cascde reaction of quinoxalinones, olefins, and sulfinic acids (Dutta et al, 2019 ).…”