Synlett, Table of Contents Synlett 2014; 25(10): 1385-1390DOI: 10.1055/s-0033-1341277 letter © Georg Thieme Verlag Stuttgart · New YorkA General and Highly Efficient Protocol for the Synthesis of Chalcogenoacetylenes by Copper(I)-Terpyridine Catalyst Authors Author Affiliations Barahman Movassagh* Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran Email: bmovass1178@yahoo.com Email: momeni@kntu.ac.ir Ali Yousefi Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran Email: bmovass1178@yahoo.com Email: momeni@kntu.ac.ir Badri Zaman Momeni* Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran Email: bmovass1178@yahoo.com Email: momeni@kntu.ac.ir Sepideh Heydari Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran Email: bmovass1178@yahoo.com Email: momeni@kntu.ac.ir Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract A highly efficient copper-catalyzed Csp–X (X = S, Se, Te) bond-forming reaction of terminal alkynes and diorganyl dichalcogenides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 4′-(4-methoxyphenyl)-2,2′:6′,2′′-terpyridine as a ligand, and K3PO4 as a base. A variety of the functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. Key words Key wordsalkynyl chalcogenides - diorganyl dichalcogenides - terminal alkynes - terpyridines - copper-catalyzed reaction Full Text References References and Notes 1a Organoselenium Chemistry – Modern Developments in Organic Synthesis. In Topics in Current Chemistry. Vol. 208. Wirth T. 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Synlett 2005; 1251 33 General Procedure To the suspension of K3PO4 (2.0 mmol) in dry DMSO (4 mL) diorganyl dichalcogenide (1.0 mmol) and terminal acetylene (2.0 mmol) were added, and the mixture was stirred at 50 °C. Then, CuI (1.0 mol%) and Mtpy (1.0 mol%) were added to the above mixture, and the reaction mixture was stirred at that temperature under aerobic conditions. The progress of the reaction was monitored by TLC. When the reaction was complete, the mixture was poured into H2O (15 mL) and extracted with EtOAc (2 × 15 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo to give the crude product which was further purified by preparative TLC (silica gel, n-hexane–EtOAc = 9:1). The identity and purity of the products were confirmed by IR, 1H NMR, and 13C NMR spectroscopic analysis. Phenyl(2-phenylethynyl)selane (3a) Yellow oil. IR (neat): ν = 2200 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.61 (d, J = 9 Hz, 2 H), 7.50–7.51 (m, 2 H), 7.32–7.37 (m, 6 H). 13C NMR (75 MHz, CDCl3): δ = 131.7, 129.5, 129.0, 128.9, 128.6, 128.3, 127.1, 123.2, 102.9, 69.2. (4-Methoxyphenyl)(2-phenylethynyl)selane (3b) Yellow oil. IR (neat): ν = 2208 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.58 (d, J = 8.8 Hz, 2 H), 7.34–7.48 (m, 5 H), 6.88 (d, J = 8.8 Hz, 2 H), 3.82 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 159.7, 133.7, 131.9, 128.6, 128.1, 121.1, 120.2, 115.0, 101.1, 70.4, 55.3. Benzyl(2-phenylethynyl)selane (3e) Yellow oil. IR (neat): ν = 2156 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.22–7.42 (m, 10 H), 3.74 (s, 2 H). 13C NMR (75 MHz, CDCl3): δ = 139.2, 137.5, 132.4, 131.4, 129.1, 128.2, 126.7, 123.5, 101.3, 68.1, 32.7. Methyl(2-phenylethynyl)selane (3f) Orange oil. IR (neat): ν = 2201 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.96–7.99 (m, 2 H), 7.86–7.89 (m, 3 H), 2.28 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 135.2, 129.99, 129.97, 125.1, 103.3, 73.2, 8.7. (Hex-1-ynyl)(phenyl)selane (3g) Yellow oil. IR (neat): ν = 2197 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.52 (d, J = 8.2 Hz, 2 H), 7.21–7.31 (m, 3 H), 2.47 (t, J = 6.9 Hz, 2 H), 1.61 (quin, J = 6.8 Hz, 2 H), 1.47 (sext, J = 7.2 Hz, 2 H), 0.94 (t, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 133.0, 129.4, 128.6, 126.7, 104.7, 57.3, 30.8, 21.98, 20.3, 14.1, 13.6. 3-(Phenylselanyl)prop-2-yn-1-ol (3i) Yellow oil. IR (neat): ν = 3339, 3059 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.51–7.63 (m, 2 H), 7.26–7.37 (m, 3 H), 4.15 (s, 2 H), 1.96 (br s, 1 H). 13C NMR (75 MHz, CDCl3): δ = 132.3, 130.3, 129.4, 127.6, 101.5, 67.5, 64.9. Phenyl(2-phenylethynyl)sulfane (3k) Yellow oil. IR (neat): ν = 2215 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.51–7.64 (m, 2 H), 7.31–7.41 (m, 2 H), 7.18–7.29 (m, 6 H). 13C NMR (75 MHz, CDCl3): δ = 134.7, 130.6, 129.37, 129.30, 129.1, 128.9, 126.7, 125.9, 98.5, 70.2. (Oct-1-ynyl)(phenyl)sulfane (3l) Yellow oil. IR (neat): ν = 2220 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.58 (d, J = 8.6 Hz, 2 H), 7.27–7.37 (m, 3 H), 2.26 (t, J = 7.2 Hz, 2 H), 1.51 (quin, J = 7.4 Hz, 2 H), 1.21–1.30 (m, 6 H), 0.86 (t, J = 6.5 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 130.5, 129.7, 129.1, 126.7, 106.1, 61.7, 37.1, 31.5, 28.5, 22.5, 14.1.Ethyl 3-(Phenylthio)propiolate (3n) Colorless oil. IR (neat): ν = 1678 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.30–7.38 (m, 3 H), 7.21–7.27 (m, 2 H), 4.55 (q, J = 6.9 Hz, 2 H), 1.54 (t, J = 6.9 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 150.2, 130.4, 129.3, 128.1, 75.7, 74.1, 60.9, 15.1. (2-Phenylethynyl)(p-tolyl)tellane (3p) Orange oil. IR (neat): ν = 2210 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.27–7.59 (m, 9 H), 2.44 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 131.7, 129.5, 129.1, 128.8, 128.4, 128.2, 127.0, 123.1, 100.8, 64.3, 22.9. Ethyl 3-(Phenyltellanyl)propiolate (3r) Pale yellow oil. IR (neat): ν = 1674 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.35–7.36 (m, 5 H), 4.27 (q, J = 7.2 Hz, 2 H), 1.33 (t, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 149.9, 133.3, 129.3, 128.2, 74.1, 73.0, 60.5, 14.3. Supplementary Material Supplementary Material Supporting Information (PDF) (opens in new window)
