Nano Copper Oxide Catalyzed Synthesis of Symmetrical Diaryl Selenides via Cascade Reaction of KSeCN with Aryl Halides

Abstract

An unprecedented transfer of selenium ion from potassium selenocyanate was observed in C-Se cross-coupling reaction catalyzed by copper oxide nanoparticles under ligand-free conditions. Utilizing this protocol wide range of symmetrical diaryl selenides were obtained in excellent yields. Nano-CuO is recyclable up to four cycles without loss of catalytic activity.

aryl halides - potassium selenocyanate - cross-coupling - nano copper oxide - ligand-free conditions - recyclable

References and Notes

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17

General Procedure for the Synthesis of Diaryl Selenides
To a stirred solution of aryl halides (2.0 mmol) and potassium selenocyanate (1.2 equiv) in dry DMSO (2.0 mL) at r.t. was added nano-CuO (5.0 mol%) followed by KOH (2.0 equiv) and heated at 110 ˚C for 15 h. The progress of the reaction was monitored by TLC. After the reaction was complete, the reaction mixture was allowed to cool, and a 1:1 mixture of EtOAc-H₂O (20 mL) was added. The combined organic extracts were washed with brine and H₂O and dried with anhyd Na₂SO₄. The solvent and volatiles were completely removed under vacuum to give the crude product, which was purified by column chromatography on silica gel (PE-EtOAc) to afford the corresponding coupling product in excellent yields.
Recycling of the Catalyst After the reaction was complete, the reaction mixture was allowed to cool, a 1:1 mixture of EtOAc- H₂O (2.0 mL) was added, and CuO was removed by centrifugation. After each cycle, the catalyst was recovered by simple centrifugation, washing with deionized H₂O and EtOAc and then drying in vacuo. The recovered nano-CuO was used directly in the next cycle. Dinaphthalen-1-ylselane (Table 2, Entry 11) Yellow liquid. IR (neat): ν = 3091, 2928, 1588, 1390, 1077, 968, 848 cm^-¹. ^¹H NMR (200 MHz, CDCl₃, TMS): δ = 8.05-8.02 (m, 4 H), 7.79-7.65 (m, 4 H), 7.55-7.40 (m, 4 H), 7.15 (t, 2 H, J = 7.93Hz). ^¹³C NMR (50 MHz, CDCl₃, TMS): δ = 137.2, 133.9, 131.9, 128.8, 128.3, 127.5, 126.6, 125.6. ESI-MS: m/z = 335 [M + 1]. Anal. Calcd for C₂₀H₁₄Se(334): C, 72.07; H, 4.23. Found: C, 72.01; H, 4.18.
Bis[4-(benzyloxy)phenyl]selane (Table 2, Entry 13) Colorless oil. IR (neat): ν = 3099, 2923, 1598, 1397, 1081, 961, 842 cm^-¹. ^¹H NMR (200 MHz, CDCl₃, TMS): δ = 7.51 (d, 4 H, J = 9.16 Hz), 7.39-7.25 (m, 10 H), 6.70 (d, 4H, J = 9.16 Hz), 5.02 (s, 4 H). ^¹³C NMR (50 MHz, CDCl₃, TMS): δ = 158.63, 138.35, 136.35, 128.52, 128.11, 127.30, 117.53, 69.87. ESI-MS: m/z = 447 [M + 1]. Anal. Calcd for C₂₆H₂₂O₂Se(446): C, 70.11; H, 4.98. Found: C, 70.04; H, 4.91.
Dipyridin-3-ylselane (Table 2, Entry 18) ^¹H NMR (200 MHz, CDCl₃): δ = 8.69 (s, 2 H), 8.58-8.52 (m, 2 H), 7.73 (d, 2 H, J = 7.93 Hz), 7.25-7.19 (m, 2 H). ^¹³C NMR (50 MHz, CDCl₃, TMS): δ = 153.3, 148.9, 140.6, 124.4. ESI-MS: m/z = 237 [M + 1]. Anal. Calcd for C₁₀H₈N₂Se(236): C, 51.08; H, 3.43; N, 11.91. Found: C, 51.14; H, 3.46; N, 11.95. Dipyrimidin-5-ylselane (Table 2, Entry 20) Colorless oil. IR (neat): ν = 3092, 2960, 1597, 1444, 1068, 865, 738 cm^-¹. ^¹H NMR (200 MHz, CDCl₃, TMS): δ = 7.51 (s, 2 H), 7.25 (s, 4 H). ^¹³C NMR (50 MHz, CDCl₃, TMS):
δ = 132.9, 129.0, 127.5. ESI-MS: m/z = 239 [M + 1]. Anal. Calcd for C₈H₆N₄Se(238): C, 40.52; H, 2.55; N, 23.63. Found: C, 40.46; H, 2.45; N, 23.57.