Supporting Information
Copper-Catalyzed Semihydrogenation of Internal Alkynes with Molecular Hydrogen
Takamichi Wakamatsu, Kazunori Nagao, Hirohisa Ohmiya*, and Masaya Sawamura*
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
Table of Contents Instrumentation and Chemicals S1 Characterization Data for Alkynes S1–S2 Procedure for the Copper-Catalyzed Semihydrogenation of Alkynes S2 Characterization Data for Alkenes S3–S5 References S5 NMR Spectra S6–S31
Instrumentation and Chemicals NMR spectra were recorded on a JEOL ECX-400, operating at 400 MHz for 1H NMR and 100.5 13 1 13 MHz for C NMR. Chemical shift values for H and C are referenced to Me4Si and the residual solvent resonances, respectively. Mass spectra were obtained with Thermo Fisher Scientific Exactive, JEOL JMS-T100LP or JEOL JMS-700TZ at the Instrumental Analysis Division, Equipment Management Center, Creative Research Institution, Hokkaido University. TLC analyses were performed on commercial glass plates bearing 0.25-mm layer of Merck Silica gel 60F254. Silica gel (Kanto Chemical Co., Silica gel 60 N, spherical, neutral) was used for column chromatography. Materials were obtained from commercial suppliers or prepared according to standard procedure unless otherwise noted. CuCl was purchased from Aldrich Chemical Co., stored under nitrogen, and used as it is. NatOBu, octane and 6-dodecyne 1a were purchased from TCI Chemical Co., stored under nitrogen, and used as it is. Diphenylacetylene 1j was purchased from Wako Chemical Co., stored under nitrogen, and used as it is. 1,4-Dioxane was purchased from Kanto Chemical Co., distilled from sodium/benzophenone and stored over 4Å molecular sieves under nitrogen. Alkynes 1b1, 1e2, 1f3, 1k4, 1l5 and 1m6 were known compounds. Alkyne 1c was prepared by THP protection of 3-octyn-1-ol. Alkyne 1d7 was prepared by the reaction between the corresponding lithium acetylide and 1-butyliodide. Alkyene 1g was prepared by Corey-Fuchs reaction with 2,6-dimethoxybenzaldehyde. Alkyne 1h was prepared by Sonogashira-Hagihara cross-coupling reaction between 1-decyne and methyl 4-iodobenzoate. Alkyne 1i was prepared by Sonogashira-Hagihara cross-coupling reaction between 1-nonyne and 4-bromoiodobenzene. [(SIMes)CuCl] was prepared according to the reported procedure.8
Characterization Data for Alkynes
2-(3-Octyn-1-yloxy)tetrahydro-2H-pyran (1c)
S1 THPO C5H11 1c 1 Colorless Oil. H NMR (400MHz, CDCl3) δ 0.90 (t, J = 7.2 Hz, 3H), 1.34–1.63 (m, 8H), 1.72 (m, 1H), 1.83 (m, 1H), 2.14 (tt, J = 7.2, 2.4 Hz, 2H), 2.45 (tt, J = 7.2, 2.4 Hz, 2H), 3.48–3.55 (m, 2H), 13 3.79 (m, 1H), 3.89 (m, 1H), 4.65 (m, 1H). C NMR (100.5 MHz, CDCl3) δ 13.59, 18.38, 19.37, 20.19, 21.85, 25.42, 30.54, 31.03, 62.09, 66.20, 76.68, 81.27, 98.65. HRMS–ESI (m/z): [M+Na]+ calcd for C13H22O2Na, 233.15120; found, 233.15098.
1,3-Dimethoxy-2-(1-propyn-1-yl)benzene (1g) OMe
Me 1g OMe 1 White solid. M.p. 106–108 ˚C. H NMR (400MHz, CDCl3) δ 2.19 (s, 3H), 3.88 (s, 6H), 6.52 (d, 13 J = 8.0 Hz, 2H), 7.21 (t, J = 8.0 Hz, 1H). C NMR (100.5 MHz, CDCl3) δ 5.2, 56.0, 71.5, 94.4, + 101.9, 103.4 128.7, 161.3. HRMS–EI (m/z): [M] calcd for C11H12O2, 176.08373; found, 173.08309.
Methyl 4-(1-Decyn-1-yl)benzoate (1h)
O C8H17 MeO 1h 1 Colorless Oil. H NMR (400MHz, CDCl3) δ 0.88 (t, J = 6.8 Hz, 3H), 1.22–1.39 (m, 8H), 1.40–1.50 (m, 2H), 1.57–1.63 (m, 2H), 2.42 (t, J = 7.2 Hz, 2H), 3.90 (s, 3H), 7.41 (d, J = 8.0 Hz, 13 2H), 7.95 (d, J = 8.0 Hz, 2H). C NMR (100.5 MHz, CDCl3) δ 14.09, 19.49, 22.64, 28.56, 28.92, 29.09, 29.18, 31.82, 52.12, 80.06, 94.01, 128.75, 128.93, 129.36, 131.43, 166.65. HRMS–APCI + (m/z): [M+H] calcd for C18H25O2, 273.18491; found, 273.18480.
Procedure for the Copper-Catalyzed Semihydrogenation of Alkynes The reaction in eq. 1 is representative. In a glove box, [(SIMes)CuCl] (20.3 mg, 0.05 mmol) and t-BuONa (4.8 mg, 0.05 mmol) were placed in a Schlenk flask containing a magnetic stirring bar. Then, octane (0.8 mL), 1,4-dioxane (0.2 mL) and 6-dodecyne (1a) were added, and the Schlenk flask was sealed with a glass stopper and then removed from the glove box. The mixture was cooled to –196 ˚C. Finally, N2 atomosphere was replaced with H2 in a balloon. The resulting mixture was heated at 100 ˚C for 12 h. As the reaction proceeded, a small amount of black solid was precipitated. After 12 h stirring at 100˚C, hexane was added to the mixture. The mixture was filtered through a short plug of silica gel, which was then washed with hexane. The NMR yield (94%) and stereoselectivity (Z/E >99:1) of 2a were determined by the 1H NMR analysis (1,1,2,2-tetrachloroethane was used as an internal standard). The residue was purified by flash column chromatography (hexane) on silica gel to give 2a (70.7 mg, 0.42 mmol) in 84% isolated yield. S2
Characterization Data for Alkenes
(Z)-6-Dodecene (2a)
C5H11 C5H11
H H 2a The product 2a was purified by flash chromatography on silica gel (hexane) (84% isolated yield from 1a, Z/E >99:1). 2a was consistent with the the literature data.9
(Z)-1-Hexen-1-ylcyclohexane (2b)
C5H11
H H 2b The product 2b was purified by flash chromatography on silica gel (hexane) (68% isolated yield from 1b, Z/E >99:1). 2b was consistent with the the literature data.10
(Z)-2-(3-Octen-1-yloxy)tetrahydro-2H-pyran (2c) THPO C5H11
H H 2c The product 2c was purified by flash chromatography on silica gel (0–5% EtOAc/hexane) (77% 1 isolated yield from 1c, Z/E >99:1). Colorless oil. H NMR (400MHz, CDCl3) δ 0.87–0.92 (m, 3H), 1.29–1.36 (m, 4H), 1.49–1.62 (m, 4H), 1.71 (m, 1H), 1.82 (m, 1H), 2.05 (q, J = 6.8 Hz, 2H), 2.35 (q, J = 6.8 Hz, 2H), 3.41 (dt, J = 9.6, 6.8 Hz, 1H), 3.50 (m, 1H), 3.73 (dt, J = 9.6, 6.8 Hz, 1H), 3.85 (m, 13 1H), 4.60 (m, 1H), 5.33–5.52 (m, 2H). C NMR (100.5 MHz, CDCl3) δ 13.9, 19.5, 22.3, 25.4, 27.0, + 27.9, 30.6, 31.7, 62.2, 67.0, 98.6, 125.4, 131.9. HRMS–ESI (m/z): [M+Na] calcd for C13H24O2Na, 235.16685; found, 235.16661.
(Z)-N,N-Dibenzyl-2-hepten-1-amine (2d)
Bn2N C4H9
H H 2d The product 2d was purified by flash chromatography on silica gel (0–5% EtOAc/hexane) (77% isolated yield from 1d, Z/E 87:13). 2d was consistent with the the literature data.11
(Z)-1-Methoxy-2-(1-propen-1-yl)benzene (2e)10
S3
Me MeO H H 2e The product 2e was purified by flash chromatography on silica gel (0–5% EtOAc/hexane) (60% 1 isolated yield from 1d, Z/E 97:3). Colorless Oil. H NMR (400MHz, CDCl3) δ 1.83 (dd, J = 7.6, 1.6 Hz, 3H), 3.84 (s, 3H), 5.84 (dq, J = 11.6, 7.6 Hz, 1H), 6.54 (dd, J = 11.6, 1.6 Hz, 1H), 6.87–6.96 13 (m, 2H), 7.19–7.28 (m, 2H). C NMR (100.5 MHz, CDCl3) δ 14.6, 55.4, 110.3, 119.9, 125.2, 126.2, 127.9, 130.1, 156.9.
(Z)-1-Methoxy-4-(1-propen-1-yl)benzene (2f)12 MeO
Me
H H 2f The product 2f was purified by flash chromatography on silica gel (0–5% EtOAc/hexane) (58% 1 isolated yield from 1e, Z/E 95:5). Colorless Oil. H NMR (400MHz, CDCl3) δ 1.89 (dd, J = 7.2, 2.0 Hz, 3H), 3.83 (s, 3H), 5.70 (dq, J = 11.6, 7.2 Hz, 1H), 6.37 (dd, J = 11.6, 2.0 Hz, 1H), 6.85–6.90 (m, 13 2H), 7.22–7.29 (m, 2H). C NMR (100.5 MHz, CDCl3) δ 14.6, 55.2, 113.5, 125.1, 129.2, 130.0, 130.3, 158.1.
(Z)-1,3-Dimethoxy-2-(1-propen-1-yl)benzene (2g)
OMe Me MeO H H 2g The product 2g was purified by flash chromatography on silica gel (0–10% EtOAc/hexane) (36% 1 isolated yield from 1g, Z/E >99:1). H NMR (400MHz, CDCl3) δ 1.58 (dd, J = 7.2, 2.0 Hz, 3H), 3.83 (s, 6H), 5.95 (dq, J = 11.2, 7.2 Hz, 1H), 6.24 (dd, J = 11.2, 2.0 Hz, 1H), 6.58 (d, J = 8.4 Hz, 13 2H), 7.21 (t, J = 8.4 Hz, 1H). C NMR (100.5 MHz, CDCl3) δ 15.5, 55.6, 103.6, 114.7, 121.0, + 128.1, 129.3, 157.7. HRMS–EI (m/z): [M] calcd for C11H14O2, 178.09938; found, 178.09889.
(Z)-Methyl 4-(1-Decen-1-yl)benzoate (2h)
O MeO
C8H17
H H 2h The product 2h was purified by flash chromatography on silica gel (0–10% EtOAc/hexane) (66% 1 isolated yield from 1f, Z/E 93:7). Colorless oil. H NMR (400MHz, CDCl3) δ 0.87 (t, J = 7.2 Hz, 3H), 1.23–1.48 (m, 12H), 2.32 (qd, J = 7.6, 2.0 Hz, 2H), 3.91 (s, 3H), 5.77 (dt, J = 12.0, 7.6 Hz, 1H), S4
13 6.42 (dd, J = 12.0, 2.0 Hz, 1H), 7.33 (m, 2H), 8.00 (m, 2H). C NMR (100.5 MHz, CDCl3) δ 14.1, 22.6, 28.7, 29.2, 29.2, 29.4, 29.8, 31.8, 52.0, 127.9 (× 2C), 128.6, 135.5 (× 2C), 142.5, 167.0. + HRMS–APCI (m/z): [M+H] calcd for C18H27O2, 275.20056; found, 275.20025.
(Z)-1,2-Diphenylethene (2j)
H H 2j The product 2j was purified by flash chromatography on silica gel (hexane) (80% isolated yield from 1j, Z/E 92:8). 2j was consistent with the the literature data.9
(Z)-3-Styrylpyridine (2m)
N
H H 2m The product 2m was purified by flash chromatography on silica gel (3–15% EtOAc/hexane) (88% isolated yield from 1m, Z/E 90:10). 2m was consistent with the the literature data.13
References 1. Lu, B.; Li, C.; Zhang, L. A. J. Am. Chem. Soc. 2010, 132, 14070–14072. 2. Barton, T. J.; Groh, B. L. J. Org. Chem. 1985, 50, 158–166. 3. An, D.-L.; Zhang, Z.; Orita, A.; Mineyama, H.; Otera, J. Synlett 2007, 1909–1912. 4. Park, S. B.; Alper, H. Chem. Commun. 2004, 1306–1307. 5. Begler, C.; Plietker, B. Chem. Commun. 2012, 5419–5421. 6. Chen, H.-J.; Lin, Z.-Y.; Li. M.-Y.; Lian, R.-J.; Xue, Q.-W.; Chung, J.-L.; Chen, S.-C.; Chen, Y.-J. Tetrahedron 2010, 66, 7755–7761. 7. Feng, H.; Jia, H.; Sun, Z. J. Org. Chem. 2014, 79, 11812–11818. 8. Santoro, O.; Collado, A.; Slawin. A. M. Z.; Nolan, S. P.; Cazin, C. S. J. Chem. Commun. 2013, 49, 10483–10485. 9. Semba, K.; Kameyama, R.; Nakao, Y. Synlett 2015, 26, 318–322. 10. Cahiez, G.; Avedissian, H. Synthesis 1998, 1199–1205. 11. Wang. M.; Xie, Y.; Li, J.; Huang, H. Synlett 2014, 2781–2786. 12. Buss, A. D.; Warren, S. J. Chem. Soc. Perkin Trans. 1 1985, 2307–2325. 13. Dong, D.-J.; Li, H.-H.; Tian, S.-K. J. Am. Chem. Soc. 2010, 132, 5018–5020.
S5
THPO C5H11 1c
Figure S1. 1H NMR spectrum of 1c S 6 THPO C5H11 1c
Figure S2. 13C NMR spectrum of 1c S 7 OMe
Me 1g OMe
Figure S3. 1H NMR spectrum of 1g S 8 OMe
Me 1g OMe
Figure S4. 13C NMR spectrum of 1g S 9 O C8H17 MeO 1h
Figure S5. 1H NMR spectrum of 1h S 10 O C8H17 MeO 1h
Figure S6. 13C NMR spectrum of 1h S 11 C5H11 C5H11
H H 2a
Figure S7. 1H NMR spectrum of 2a S 12 C5H11 C5H11
H H 2a
Figure S8. 13C NMR spectrum of 2a S 13 C5H11
H H 2b
Figure S9. 1H NMR spectrum of 2b S 14 C5H11
H H 2b
Figure S10. 13C NMR spectrum of 2b S 15 THPO C5H11
H H 2c
Figure S11. 1H NMR spectrum of 2c S 16 THPO C5H11
H H 2c
Figure S12. 13C NMR spectrum of 2c S 17 Bn2N C4H9
H H 2d
Figure S13. 1H NMR spectrum of 2d S 18 Bn2N C4H9
H H 2d
Figure S14. 13C NMR spectrum of 2d S 19 Me MeO H H 2e
Figure S15. 1H NMR spectrum of 2e S 20 Me MeO H H 2e
Figure S16. 13C NMR spectrum of 2e S 2 1 MeO
Me
H H 2f
Figure S17. 1H NMR spectrum of 2f S 22 MeO
Me
H H 2f
Figure S18. 13C NMR spectrum of 2f S 23 OMe Me MeO H H 2g
Figure S19. 1H NMR spectrum of 2g S 24 OMe Me MeO H H 2g
Figure S20. 13C NMR spectrum of 2g S 25 O MeO
C8H17
H H 2h
Figure S21. 1H NMR spectrum of 2h S 26 O MeO
C8H17
H H 2h
Figure S22. 13C NMR spectrum of 2h S 27 H H 2j
Figure S23. 1H NMR spectrum of 2j S 28 H H 2j
Figure S24. 13C NMR spectrum of 2j S 29 N
H H 2m
Figure S25. 1H NMR spectrum of 2m S 30 N
H H 2m
Figure S26. 13C NMR spectrum of 2m S 31