Copper-Catalyzed Semihydrogenation of Alkynes to Z-Alkenes

Kazuhiko Semba; Ryohei Kameyama; Yoshiaki Nakao

doi:10.1055/s-0034-1379896

Synlett, Table of Contents

Synlett 2015; 26(03): 318-322
DOI: 10.1055/s-0034-1379896

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Copper-Catalyzed Semihydrogenation of Alkynes to Z-Alkenes

Authors

Kazuhiko Semba*

^aDepartment of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, Kyoto 615-8510, Japan
Ryohei Kameyama

^aDepartment of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, Kyoto 615-8510, Japan
Yoshiaki Nakao*

^aDepartment of Material Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-Ku, Kyoto 615-8510, Japan

^bCREST, 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

Abstract

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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.

Key words

alkynes - alkenes - catalysis - copper - hydrogenation

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References

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; R_f = 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; R_f = 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:

10a Goeden GV, Caulton KG. J. Am. Chem. Soc. 1981; 103: 7354

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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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Supplementary Material

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