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Synlett 2014; 25(10): 1385-1390
DOI: 10.1055/s-0033-1341277
DOI: 10.1055/s-0033-1341277
letter
A General and Highly Efficient Protocol for the Synthesis of Chalcogenoacetylenes by Copper(I)-Terpyridine Catalyst
Further Information
Publication History
Received: 04 February 2014
Accepted after revision: 31 March 2014
Publication Date:
12 May 2014 (online)
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
alkynyl chalcogenides - diorganyl dichalcogenides - terminal alkynes - terpyridines - copper-catalyzed reactionSupporting Information
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10.1055/s-00000083.
- Supporting Information
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- 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.