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Synlett 2016; 27(13): 1969-1972
DOI: 10.1055/s-0035-1561864
DOI: 10.1055/s-0035-1561864
letter
Ruthenium(II)-Catalyzed Hydration of Terminal Alkynes in PEG-400
Further Information
Publication History
Received: 28 March 2016
Accepted after revision: 23 April 2016
Publication Date:
18 May 2016 (online)
![](https://www.thieme-connect.de/media/synlett/201613/lookinside/thumbnails/st-2016-d0217-l_10-1055_s-0035-1561864-1.jpg)
Abstract
The ruthenium(II)-catalyzed hydration of terminal alkynes in PEG-400 to yield methyl ketones through Markovnikov addition of water across alkyne is reported.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561864.
- Supporting Information
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References and Notes
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- 17 General Procedure for Hydration of Terminal Alkynes in PEG-400: To a solution of alkyne (1.0 mmol) in PEG-400/H2O (4:1) was added [Ru(p-cymene)Cl2]2 (0.01 mmol), and the mixture stirred at room temperature. Upon completion of the reaction (monitoring by TLC), the reaction mixture was diluted with Et2O (10 mL), stirred for 10 min, and allowed to stand in an ice-salt bath to solidify the PEG-400. The organic layer was decanted, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue obtained was purified by silica gel flash column chromatography (ethyl acetate–petroleum ether) to give the pure product. 4-(Benzyloxy)butan-2-one (2a): Prepared according to the general procedure and purified by flash chromatography (EtOAc–hexanes, 10%). Yield: 63%; green liquid. 1H NMR (400 MHz, CDCl3): δ = 7.56–7.02 (m, 5 H), 4.51 (s, 2 H), 3.73 (t, J = 6.3 Hz, 2 H), 2.71 (t, J = 6.3 Hz, 2 H), 2.17 (s, 3 H). 13C NMR (126 MHz, CDCl3): δ = 207.2, 138.1, 128.4, 127.7, 73.3, 65.3, 43.8, 30.5. IR (neat): 2925, 2855, 1721, 1458, 1275, 1110, 707 cm–1. HRMS (ESI): m/z [M + H]+ calcd for C11H15O2: 179.1066; found: 179.1065. 4-Oxopentanoic Acid (2g): Prepared according to the general procedure and purified by flash chromatography (EtOAc–hexanes, 10%). Yield: 92%; colorless oil. 1H NMR (300 MHz, CDCl3): δ = 9.25 (s, 1 H), 2.75 (t, J = 6.4 Hz, 2 H), 2.61 (t, J = 6.4 Hz, 2 H), 2.19 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 207.1, 178.5, 37.7, 29.8, 27.8. IR (neat): 2923, 2854, 1708, 1404, 1367, 1165, 555 cm–1. HRMS (ESI): m/z [M + H]+ calcd for C5H9O3: 117.0546; found: 117.0557. 4-Methyl-4-(3-oxobutoxy)cyclohexa-2,5-dienone (2j): Prepared according to the general procedure and purified by flash chromatography (EtOAc–hexanes, 50%). Yield: 78%; dark-green oil. 1H NMR (300 MHz, CDCl3): δ = 6.72 (d, J = 10.2 Hz, 2 H), 6.23 (d, J = 10.2 Hz, 2 H), 3.50 (t, J = 6.0 Hz, 2 H), 2.57 (t, J = 6.0 Hz, 2 H), 2.11 (s, 3 H), 1.33 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 205.4, 184.1, 150.8, 129.2, 71.5, 59.5, 42.8, 29.6, 25.4. IR (neat): 2927, 1712, 1669, 1389, 1176, 1087, 863, 701 cm–1. HRMS (ESI): m/z [M + H]+ calcd for C11H15O3: 195.1015; found: 195.1019. 2-Methyl-2-(2-oxopropyl)cyclopentane-1,3-dione (2k): Prepared according to the general procedure and purified by flash chromatography (EtOAc–hexanes, 50%). Yield: 81%; colorless oil. 1H NMR (400 MHz, CDCl3): δ = 3.10 (s, 2 H), 2.92–2.71 (m, 4 H), 2.00 (s, 3 H), 0.98 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 216.4, 206.3, 52.4, 51.7, 34.7, 28.2, 19.3. IR (neat): 2926, 2856, 1718, 1455, 1390, 1183, 1074, 802, 548 cm–1. HRMS (ESI): m/z [M + H]+ calcd for C9H13O3: 169.0859; found: 169.0855.