A Highly Efficient Copper-Catalyzed Synthesis of Unsymmetrical Diaryl- and Aryl Alkyl Chalcogenides from Aryl Iodides and Diorganyl Disulfides and Diselenides

Abstract

An efficient and convenient protocol has been developed for the copper-catalyzed reaction of aryl iodides and diorganyl disulfides and diselenides. A variety of symmetrical and unsymmetrical diaryl- and aryl alkyl chalcogenides were synthesized with good functional group tolerance and chemoselectivity by using copper(Ι) iodide as a catalyst, 4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine as ligand, and KOH as base under an inert atmosphere.

Key words

cross-coupling - diaryl chalcogenides - copper-catalyzed reaction - aryl halides - dichalcogenides

• References and Notes

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• 24e Reddy VP, Kumar AV, Swapna K, Rao KR. Org. Lett. 2009; 11: 951. Di-p-tolyl Sulfide White solid; mp 55–57 °C; ¹H NMR (300 MHz, CDCl₃): δ = 7.30 (d, J = 8.4 Hz, 4 H), 7.16 (d, J = 8.4 Hz, 4 H), 2.38 (s, 6 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 136.9, 132.7, 131.1, 130.0, 21.1. 4-Methoxyphenyl Phenyl Sulfide Colorless oil; ¹H NMR (300 MHz, CDCl₃): δ = 7.49 (dt, J = 6.9, 1.8 Hz, 2 H), 7.19–7.29 (m, 5 H), 6.96 (dt, J = 6.9, 1.8 Hz, 2 H), 3.85 (s, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 159.8, 138.6, 135.3, 128.9, 128.2, 125.7, 124.3, 115.0, 55.3. Naphthalen-2-yl p-Tolyl Sulfide White solid; mp 69–71 °C; ¹H NMR (300 MHz, CDCl₃): δ = 7.75–7.86 (m, 4 H), 7.41–7.52 (m, 5 H), 7.21 (d, J = 9.0 Hz, 2 H), 2.42 (s, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 137.6, 134.3, 133.7, 132.1, 132.0, 131.4, 130.1, 128.7, 128.3, 127.9, 127.7, 127.3, 126.5, 125.9, 21.1. 4-Methoxyphenyl Octyl Sulfide Colorless oil; ¹H NMR (300 MHz, CDCl₃): δ = 7.34 (dt, J = 9.9, 2.1 Hz, 2 H), 6.85 (dt, J = 9.9, 2.1 Hz, 2 H), 3.80 (s, 3 H), 2.82 (t, J = 6 Hz, 3 H), 1.54–1.63 (m, 2 H), 1.27–1.41 (m, 12 H), 0.88 (t, J = 6 Hz, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 158.6, 132.8, 126.9, 114.4, 55.2, 35.7, 31.7, 29.3, 29.14, 29.11, 28.6, 22.6, 14.0. 1-[4-(Phenylthio)phenyl]ethanone Yellow solid; mp 62–64 °C; ¹H NMR (300 MHz, CDCl₃): δ = 7.82 (d, J = 8.4 Hz, 2 H), 7.48–7.50 (m, 2 H), 7.39–7.41 (m, 3 H), 7.21 (d, J = 8.4 Hz, 2 H), 2.55 (s, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 197.1, 144.9, 134.4, 133.9, 132.0, 129.7, 128.9, 128.8, 127.4, 26.5. 4-Cyanophenyl Phenyl Sulfide Colorless oil; ¹H NMR (300 MHz, CDCl₃): δ = 7.58–7.64 (m, 4 H), 7.50–7.26 (m, 5 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 141.1, 139.5, 133.4, 129.7, 128.7, 127.2, 127.1, 118.0, 110.8. 4-Chlorophenyl p-Tolyl Sulfide White solid; mp 69–70 °C; ¹H NMR (300 MHz, CDCl₃): δ = 7.33 (d, J = 8.2 Hz, 2 H), 7.17–7.24 (m, 6 H), 2.35 (s, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 138.0, 136.0, 132.5, 132.3, 130.8, 130.7, 130.2, 129.1, 21.2. 2-(Butylthio)thiophene Colorless oil; ¹H NMR (300 MHz, CDCl₃): δ = 7.20–7.29 (m, 3 H), 2.82 (t, J = 6.0 Hz, 2 H), 1.27–1.34 (m, 4 H), 0.84–0.91 (m, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 139.9, 132.9, 129.5, 127.8, 53.3, 34.2, 22.4, 13.9. Diphenyl Sulfide Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 7.40 (d, J = 8.0 Hz, 4 H), 7.35 (t, J = 8.0 Hz, 4 H), 7.30 (t, J = 8.0 Hz, 2 H); ¹³C NMR (100.6 MHz, CDCl₃): δ = 135.9, 131.1, 129.3, 127.1. Naphthalen-2-yl Phenyl Sulfide White solid; mp 63–65 °C; ¹H NMR (300 MHz, CDCl₃): δ = 7.91 (s, 1 H), 7.77–7.83 (m, 3 H), 7.43–7.53 (m, 5 H), 7.27–7.37 (m, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 135.9, 133.8, 133.0, 132.3, 131.0, 129.9, 129.3, 128.9, 128.8, 127.8, 127.4, 127.1, 126.6, 126.2. Benzyl Phenyl Sulfide White solid; mp 53–55 °C; ¹H NMR (300 MHz, CDCl₃): δ = 7.24–7.40 (m, 10 H), 4.18 (s, 2 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 137.5, 136.4, 129.8, 128.9, 128.5, 127.2, 126.3, 36.0. 4-Bromophenyl Phenyl Sulfide Colorless oil; ¹H NMR (300 MHz, CDCl₃): δ = 7.60 (dt, J = 6.0, 2.7 Hz, 1 H), 7.24–7.44 (m, 6 H), 7.19 (dt, J = 6.0, 2.7 Hz, 1 H), 7.05 (dt, J = 6.0, 2.7 Hz, 1 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 135.4, 134.7, 133.0, 131.9, 131.7, 129.3, 127.6, 120.8. Phenyl o-Tolyl Sulfide Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 7.28–7.54 (m, 5 H), 7.26 (d, J = 8.0 Hz, 3 H), 7.19 (t, J = 8.0 Hz, 1 H), 2.43 (s, 3 H); ¹³C NMR (100.6 MHz, CDCl₃): δ = 140.0, 136.2, 133.8, 133.1, 131.1, 130.7, 129.7, 129.3, 126.8, 126.4, 20.7. 4-Methylphenyl Phenyl Sulfide Colorless oil; ¹H NMR (300 MHz, CDCl₃): δ = 7.41–7.43 (m, 5 H), 7.20–7.32 (m, 4 H), 2.42 (s, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 137.61, 137.2, 132.3, 131.3, 130.1, 129.8, 129.0, 126.4, 21.1. 4-Methoxyphenyl Phenyl Selenide Yellow oil; ¹H NMR (300 MHz, CDCl₃): δ = 7.55 (dd, J = 6.9, 2.1 Hz, 2 H), 7.39 (dd, J = 7.38, 1.4 Hz, 2 H), 7.21–7.29 (m, 3 H), 6.90 (dd, J = 6.9, 2.1 Hz, 2 H), 3.84 (s, 3 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 159.8, 136.6, 133.2, 130.9, 129.2, 126.4, 119.9, 115.1, 55.3. 2-Methoxyphenyl Phenyl Selenide Yellow oil; ¹H NMR (500 MHz, CDCl₃): δ = 7.27–7.70 (m, 5 H), 7.08–7.10 (m, 1 H), 6.88–6.95 (m, 3 H), 3.95 (s, 3 H); ¹³C NMR (125 MHz, CDCl₃): δ = 157.1, 135.9, 131.3, 130.0, 128.8, 128.6, 128.3, 122.4, 122.1, 110.9, 56.4. 4-Methylphenyl Phenyl Selenide Yellow oil; ¹H NMR (500 MHz, CDCl₃): δ = 7.56 (d, J = 7.6 Hz, 4 H), 7.36 (d, J = 6.4 Hz, 3 H), 7.23 (d, J = 7.6 Hz, 2 H), 2.46 (s, 3 H); ¹³C NMR (125 MHz, CDCl₃): δ = 138.2, 134.5, 134.4, 132.5, 132.6, 130.7, 129.8, 127.4, 21.7. 4-Chlorophenyl Phenyl Selenide Yellow oil; ¹H NMR (500 MHz, CDCl₃): δ = 7.55–7.79 (m, 4 H), 7.17–7.37 (m, 5 H); ¹³C NMR (125 MHz, CDCl₃): δ = 134.8, 134.6, 134.0, 133.7, 131.2, 130.0, 129.9, 128.1.