Synlett 2015; 26(03): 318-322
DOI: 10.1055/s-0034-1379896
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© Georg Thieme Verlag Stuttgart · New York

Copper-Catalyzed Semihydrogenation of Alkynes to Z-Alkenes

Kazuhiko Semba*
a  Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, Kyoto 615-8510, Japan
,
Ryohei Kameyama
a  Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, Kyoto 615-8510, Japan
,
Yoshiaki Nakao*
a  Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, Kyoto 615-8510, Japan
b  CREST, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan   Email: semba.kazuhiko.5n@kyoto-u.ac.jp   Email: nakao.yoshiaki.8n@kyoto-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 16 December 2014

Accepted after revision: 20 January 2015

Publication Date:
26 January 2015 (online)


Abstract

Copper-catalyzed semihydrogenation of internal alkynes has been developed. The reaction proceeds under an atmosphere of hydrogen (5 atm) at 100 °C in the presence of a readily available [(PPh3)CuCl]4 catalyst to give various Z-alkenes stereoselectively.

Supporting Information

 
  • References and Notes

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  • 9 General Procedure for the Copper-Catalyzed Semihydro­genationIn a glove box, [(PPh3)CuCl]4 (7.2 mg, 5.0 μmol), toluene (1.0 mL), LiOt-Bu (40 mg, 0.50 mmol), and i-PrOH (60 mg, 1.0 mmol) were added to a vial in this order. After being stirred for 1 min at r.t., alkyne 1 (1.0 mmol) and toluene (2.0 mL) were added to the resulting mixture. The vial was placed in an autoclave, and the autoclave was taken out of the glove box. An N2 atmosphere in the autoclave was purged by positive pressure of H2. Then, the mixture was stirred at 100 °C for 3 h under H2 (5 atm). After being cooled to r.t., H2 was released, and the mixture was diluted with EtOAc. The conversion of alkynes was determined by GC analysis with n-tridecane as an internal standard. The resulting solution was filtered through a pad of silica gel, and the filtrate was concentrated. The residue was purified by medium-pressure column chromatography on silica gel to give (Z)-2.Representative data:(Z)-2d: The reaction of 1d (180 mg, 1.0 mmol) at 60 °C followed by purification by MPLC (16 g of silica gel and Biotage® SNAP Ultra 10 g; n-hexane) gave the corresponding product (160 mg, 0.91 mmol, 91%) as a mixture of (Z)-2d,14a (E)-2d,14b and 3d 14c [(Z)-2d/(E)-2d/3d = 95:5:<1 determined by 1H NMR analysis] as a colorless oil; Rf = 0.53 (hexane). 1H NMR (CDCl3, 400 MHz): δ = 7.28–7.16 (m, 10 H), 6.60 (s, 2 H); 13C NMR (CDCl3, 101 MHz): δ = 137.2, 130.2, 128.8, 128.2, 127.1. All the resonances of 1H and 13C NMR spectra were consistent with reported values.14a (Z)-2g: The reaction of 1g (79 mg, 0.30 mmol) at 80 °C in toluene (0.80 mL) followed by purification by MPLC (16 g of silica gel and Biotage® SNAP Ultra 10 g; n-hexane–EtOAc, 99:1 to 93:7) gave the corresponding product (Z)-2g (42 mg, 0.16 mmol, 52%) as a pale yellow oil; Rf = 0.35 (n-hexane–EtOAc, 95:5). 1H NMR (CDCl3, 400 MHz): δ = 7.90 (d, J = 8.5 Hz, 2 H), 7.30 (d, J = 8.5 Hz, 2 H), 7.25–7.20 (m, 5 H), 6.71 (d, J = 12.2 Hz, 1 H), 6.61 (d, J = 12.2 Hz, 1 H), 5.24 (sept, J = 6.1 Hz, 1 H), 1.36 (d, J = 6.1 Hz, 6 H); 13C NMR (CDCl3, 101 MHz): δ = 165.9, 141.8, 136.7, 132.1, 129.4, 129.31, 129.28, 128.8, 128.7, 128.3, 127.4, 68.3, 21.9. HRMS–APCI (+): m/z [M + H]+ calcd for C18H19O2: 267.1380; found: 267.1375

    • [(PPh3)CuH]6 was synthesized from Cu(Ot-Bu) and Ph3P, see:
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      syn-Addition of copper hydride across internal alkynes was reported, see:
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  • 12 For a reference on protonation of an alkenyl copper with an alcohol, see ref. 2a
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