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General procedure for entries 3–6 in Table 1. In a glove box, a vial was charged with CuCl (2.0
mg, 0.020 mmol), a phosphine ligand (0.020 mmol) and toluene (1.00 mL), and the resulting
solution was stirred for 10 min at room temperature. To this vial, LiOtBu (40 mg, 0.50 mmol) and
iPrOH (60 mg, 1.0 mmol) were added in this order. After the resulting mixture was stirred for 1 min
at room temperature, 1a (160 mg, 1.0 mmol) and toluene (2.0 mL) were added. The vial was placed
in an autoclave and the autoclave was taken out of the glove box. N2 in the autoclave was replaced
with H2 by positive pressure of H2. Then, the mixture was stirred at 100 °C for 3 h under 5 atm of
H2. After cooling to room temperature, H2 was released and the mixture was diluted with EtOAc.
The conversion was determined by GC analysis with n-tridecane (18 mg, 0.10 mmol) as an internal
standard. The resulting solution was filtered through a pad of silica gel and the yields of the
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products were determined by H NMR analysis with 1,3,5-trimethoxybenzene as an internal
standard.
(Z)-2a. The reaction of 1a followed by purification by MPLC (16 g of silica gel and
Ph
Biotage® SNAP Ultra 10 g, n-hexane) gave the corresponding products (Z)-2a
(130 mg, 0.80 mmol, 80%) as a colorless oil, Rf = 0.67 (n-hexane).1H NMR
Bu
(CDCl3, 400 MHz): δ 7.37–7.22 (m, 5H), 6.43 (d, J = 11.6 Hz, 1H), 5.69 (dt, J =
11.6 Hz, 7.3 Hz, 1H), 2.35 (dq, J = 7.3 Hz, 1.8 Hz, 2H), 1.48–1.33 (m, 4H), 0.92 (t, J = 7.3 Hz,
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3H); C NMR (CDCl3, 101 MHz): δ 137.8, 133.2, 128.73, 128.68, 128.1, 126.4, 32.2, 28.3, 22.4,
14.0; All the resonances of 1H and 13C NMR spectra were consistent with reported values.4
General procedure for Table 2. Similar procedure for Table 1 was employed. The products were
purified by MPLC on silica gel to give the corresponding products. In the case of entries 1, 6, 8, and
11, the yields of (Z)-2b5a, (E)-2b,5a, 3b,5b, (Z)-2g, (Z)-2i6, and (Z)-5-dodecene7 were determined by
1H NMR analysis with 1,3,5-trimethoxybenzene as an internal standard.
(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
Ph
corresponding product (160 mg, 0.91 mmol, 91%) as a mixture of (Z)-2c,8a
Ph
1
(E)-2d,8b and 3d8c ((Z)-2d/(E)-2d/3d = 95/5/<1 determined by H NMR analysis)
as a colorless oil, Rf = 0.53 (hexane). 1H NMR (CDCl3, 400 MHz): δ 7.28–7.16 (m,
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10H), 6.60 (s, 2H); C 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.8a
(Z)-2e. The reaction of 1e (210 mg, 1.00 mmol) followed by purification by
MPLC (16 g of silica gel and Biotage® SNAP Ultra 10 g, n-hexane) gave
the corresponding product (208 mg, 0.99 mmol, 99%) as a mixture of
1
(Z)-2e,9a (E)-2e,9b and 3e9c ((Z)-2e/(E)-2e/3e = 98/<1/2 determined by H
NMR analysis) as a colorless solid, Rf = 0.59 (n-hexane). 1H NMR (CDCl3,
400 MHz): δ 7.17 (d, J = 8.1 Hz, 4H), 7.04 (d, J = 8.1 Hz, 4H), 6.50 (s, 2H),
13
2.32 (s, 6H); C NMR (CDCl3, 101 MHz): δ 136.7, 134.5, 129.5, 128.8,
128.7, 21.2. All the resonances of 1H and 13C NMR spectra were consistent with reported values.9a
4
Cahiez, G.; Gager, O.; Lecomte, F. Org. Lett. 2008, 10, 5255.
(a) Chen, C.; Dugan, T. R.; Brennessel, W. W.; Weix, D. J.; Holland, P. L. J. Am. Chem. Soc. 2014, 136, 945. (b) Carter, T. S.; Guiet, L.; Frank, D.
5
J.; West, J.; Thomas, S. P. Adv. Synth. Catal. 2013, 355, 880.
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Belger, C.; Neisius. N. M.; Plietker. B. Chem. Eur. J. 2010, 16, 12214.
Cahiez, G.; Gager, O.; Buendia, J.; Patinote, C. Chem. Eur. J. 2012, 18, 5860.
(a) Yan, M.; Jin, T.; Ishikawa, Y.; Minato, T.; Fujita, T.; Chen, L.-Y.; Bao, M.; Asao, N.; Chen, M.-W.; Yamamoto, Y. J. Am. Chem. Soc. 2012,
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134, 17536. (b) Chen, Z.; Luo, M.; Wen, Y.; Luo, G.; Liu, L. Org. Lett. 2014, 16, 3020. (c) Kantam. M. L.; Kishore. R.; Yadav, J.; Sudhakar, M.;
Venugopal, A. Adv. Synth. Catal. 2012, 354, 663.
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(a) Li. J.; Hua. R.; Liu. T. J. Org. Chem. 2010, 75, 2966. (b) Kantam, M. L.; Srinivas. P.; Yadav. J.; Likhar. P. R.; Bhargava, S. J. Org. Chem. 2009,
74, 4882. (c) Chen. T.; Yang, Li. L.; Huang. K.-W. Tetrahedron 2012, 68, 6152.
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