Copper-catalyzed selective semihydrogenation of terminal alkynes with hypophosphorous acid

Article abstract of DOI:10.1002/adsc.201300916

A novel copper-catalyzed selective semihydrogenation of terminal alkynes using hypophosphorous acid as hydrogen donor took place efficiently to afford the corresponding alkenes in high yields. A broad range of substituted terminal aromatic and aliphatic alkenes, including terminal dienes and enynes bearing internal triple bonds, can be efficiently synthesized by this reaction.

Full text of DOI:10.1002/adsc.201300916

Supporting Information
© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013

Supporting Information for
Copper-Catalyzed Selective Semihydrogenation
of Terminal Alkynes with Hypophosphorus Acid
Huanyang Cao, Tieqiao Chen,Yongbo Zhou,* Daoqing Han, Shuang-Feng Yin* and
Li-Biao Han
a State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha, 410082, People’s Republic of China
Fax: (+) 86-731-88821171; E-mail: zhouyb@hnu.edu.cn; sf_yin@hnu.edu.cn.
Contents
1. General Information...........................................................................................................................S2
2. Analytical and spectral data of products..........................................................................................S2
3. Semihydrogenation of 1-ethynyl-3,5-dimethoxybenzene with fully deuterated hypophosphorous
acid.......................................................................................................................................................S3
4. References...........................................................................................................................................S4
5. Copies of NMR spectrascopies..........................................................................................................S5
S1

1. General Information
All reactions were performed in Nitrogen atmosphere. All solvents were thoroughly degassed before use.
All other reagents were purchased from commercially sources and used without further purification. 1H
NMR and 13C NMR spectra were recorded on a Bruker Avance-Ⅲ 400 MHz spectrometer (400 MHz
1
13
1
for H NMR, 100 MHz for C NMR). CDCl3 was used as the solvent. H NMR chemical shifts are
13
reported using TMS as internal standard, C NMR chemical shifts are reported relative to CDCl3 as
internal standard. Flash column chromatography was performed over silica gel (200-300 mesh). GC
analysis was performed on a Shimadzu GC-2014 instrument with a FID detector and Rtx-1 capillary
column (30 m length, 0.32 mm inner diameter, 0.25 μm film thickness) using nitrogen as carrier gas.
2. Analytical and spectral data of products
1
4-tert-Butylstyrene (2e): Eluent: petroleum ether. Clear, colorless oil: 114.2mg (90%). H NMR (400
MHz, CDCl3) δ 7.36 (s, 4H), 6.70 (dd, J = 17.6, 10.9 Hz, 1H), 5.71 (d, J = 17.6 Hz, 1H), 5.20 (d, J =
13
10.9 Hz, 1H), 1.32 (s, 9H); C NMR (100 MHz, CDCl3): δ 149.8, 135.5, 133.8, 124.9, 124.1, 112.0,
33.5, 30.2. 1H and 13C NMR spectrum of the product were identical to that of the reference.1
4-ethenyl-4’-propyl-1,1’-Biphenyl (2f): Eluent: petroleum ether. Lignt yellow solid: 202.3 mg (91%).
1H NMR (400 MHz, CDCl3) δ 7.52 (dt, J = 19.5, 8.2 Hz, 6H), 7.25 (t, J = 4.0 Hz, 2H), 6.75 (dd, J =
17.6, 10.9 Hz, 1H), 5.78 (d, J = 17.6 Hz, 1H), 5.26 (d, J = 10.9 Hz, 1H), 2.65-2.61 (m, 2H), 1.73-1.63
13
(m, 2H), 0.98 (t, J = 7.3 Hz, 3H); C NMR (100 MHz, CDCl3): δ 140.9, 139.5, 137.0, 135.4, 135.2,
127.9, 126.0, 125.7, 125.6, 112.6, 36.7, 23.5, 12.9.
3,5-Dimethoxystyrene (2h): Eluent: petroleum ether/ethyl acetate (50:1). Colourless oil: 137.9 mg
(84%). 1H NMR (400 MHz, CDCl3) δ 6.64 (dd, J = 17.5, 10.8 Hz, 1H), 6.57 (d, J = 2.2 Hz, 2H), 6.39 (t,
J = 2.1 Hz, 1H), 5.73 (d, J = 17.5 Hz, 1H), 5.25 (d, J = 10.8 Hz, 1H), 3.79 (s, 6H); 13C NMR (100 MHz,
1
13
CDCl3): δ 160.9, 139.7, 136.9, 114.4, 104.3, 100.1, 55.3. H and C NMR spectrum of the product
were identical to that of the reference.2
4-Vinylacetophenone (2m): Eluent: petroleum ether/ethyl acetate (20:1). White Solid: 117.0 mg (80%).
1H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 8.1 Hz, 2H), 7.49 (d, J = 8.1 Hz, 2H), 6.76 (dd, J = 17.6,
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10.9 Hz, 1H), 5.89 (d, J = 17.6 Hz, 1H), 5.40 (d, J = 10.9 Hz, 1H), 2.61 (s, 3H); C NMR (100 MHz,
1
13
CDCl3): δ 196.7, 141.0, 135.2, 134.8, 127.7, 125.3, 115.7, 25.6. H and C NMR spectrum of the
product were identical to that of the reference.3
1
1,4-Divinylbenzene(DVB) (2n): Eluent: petroleum ether. Colourless oil 105.5 mg (81%). H NMR
(400 MHz, CDCl3) δ 7.37 (s, 4H), 6.70 (dd, J = 17.6, 10.9 Hz, 2H), 5.75 (d, J = 17.6, 2H), 5.24 (dd, J =
10.9, 2H); 13C NMR (100 MHz, CDCl3): δ 137.1, 136.5, 126.4, 113.8. 1H and 13C NMR spectrum of the
product were identical to that of the reference.3
Undec-10-enoic acid (2t): Eluent: petroleum ether/ethyl acetate (1:1). Colourless oil: 167.6 mg (91%).
o
o
Colourless oil. Mp.: 42 C (42 C)1H NMR (400 MHz, CDCl3) δ 11.64 (brs, 1H), 5.81 (m, 1H),
5.02-4.92 (m, 2H), 2.35 (t, J = 7.5 Hz, 2H), 2.06-2.01 (m, 2H), 1.68-1.59 (m, 2H), 1.39-1.30 (m, 10H);
1
13C NMR (100 MHz, CDCl3): δ 180.2, 139.2, 114.2, 34.1, 33.8, 29.3, 29.2, 29.1, 29.0, 28.9, 24.7. H
and 13C NMR spectrum of the product were identical to that of the reference.4
Methyl 10-undecenoate (2u): Eluent: ethyl acetate (50:1). Colourless oil: 166.6 mg (84%).1H NMR
(400 MHz, CDCl3) δ 5.81 (m, 1H), 4.96 (dd, J = 24.2, 13.6 Hz, 2H), 3.67 (s, 3H), 2.30 (t, J = 7.5 Hz,
13
2H), 2.04 (m, 2H), 1.66-1.58 (m, 2H), 1.36-1.26 (brs, 10H); C NMR (100 MHz, CDCl3): δ 174.3,
1
13
139.2, 114.1, 51.4, 34.1, 33.8, 29.3, 29.2, 29.1, 29.0, 28.9, 24.9. H and C NMR spectrum of the
product were identical to that of the reference.5
S2

N-(4-pentenyl)phthalimide (2v): Eluent: ethyl acetate (5:1). Colourless oil: 202.3 mg (94%). 1H NMR
(400 MHz, CDCl3) δ 7.85 (dd, J = 5.5, 3.0 Hz, 2H), 7.72 (dd, J = 5.5, 3.0 Hz, 2H), 5.82 (ddt, J = 16.9,
13
10.2, 6.6 Hz, 1H), 5.08-4.97 (m, 2H), 3.72-3.68 (m, 2H), 2.10-2.15 (m, 2H), 1.83-1.75 (m, 2H); C
NMR (100 MHz, CDCl3): δ 168.4, 137.3, 133.9, 132.1, 123.2, 115.3, 37.6, 31.0, 27.6. 1H and 13C NMR
spectrum of the product were identical to that of the reference.6
1
1-Hexadecen-11-yne (2x): Eluent: petroleum ether. Colourless oil: 191.6 mg (87%). H NMR (400
MHz, CDCl3) δ 5.81 (ddt, J = 16.9, 10.1, 6.7 Hz, 1H), 5.02-4.92 (m, 2H), 2.17-2.12 (m, 4H), 2.04 (q, J
= 7.0 Hz, 2H), 1.48-1.432 (m, 4H), 1,36-1.41 (m, 6H), 1.29 (s, 6H), 0.91 (t, J = 7.1 Hz, 3H); 13C NMR
(100 MHz, CDCl3): δ 138.2, 113.1, 79.2, 32.8, 30.2, 28.4, 28.1, 27.9, 27.8, 20.9, 17.7, 17.4, 12.6.
3. Semihydrogenation of 1-ethynyl-3,5-dimethoxybenzene with fully deuterated hypophosphorous
acid
Under N2 atmosphere, a mixture of 1-ethynyl-3,5-dimethoxybenzene (1.0 mmol), 50% D3PO2 in D2O
solution (2.0 mmol), copper citrate (0.05 mmol) and HMTA (0.05 mmol) in DMF (2.0 mL) was stirred
at 130 °C for 6 h. Then the reaction mixture was cooled to room temperature and ethyl acetate (30 mL)
was added. The solution was washed by saturated NH4Cl aqueous solution (2×10 mL). After removal of
the volatiles, the crude products were subject to purification by column chromatography on silica gel
using petroleum ether/ethyl acetate (50:1) as an eluent to obtain the product as a colorless oil 137.1 mg
(82%)。
S3

4. References
(1) S. E. Denmark, C. R. Butler, J. Am. Chem. Soc. 2008, 130, 3690-3704.
(2) E. Alacid, C. Nájera, J. Org. Chem. 2008, 73, 2315-2322.
(3) G. Wienhöfer, F. A. Westerhaus, R. V. Jagadeesh, K. Junge, H. Junge, M. Beller, Chem. Commun.
2012, 48, 4827-4829.
(4) A. L. II Miller, N. B. Bowden, Chem. Commun. 2007, 2051-2053.
(5) F. -L. Wu, P. R. Benjamin, P. M. Ross, Eur. J. Org. Chem. 2010, 1989-1998.
(6) E. M. Stang, M. C. White, J. Am. Chem. Soc. 2011, 133, 14892-148
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5. Copies of NMR spectrascopies
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