Z-Selective Ru-Catalyzed Semireduction of Alkynes
FULL PAPER
32.4, 31.9, 27.0, 26.9, 25.9, 22.4, 14.0 ppm; IR (film): n˜ =3331 (b), 2954
(m), 2926 (s), 2858 (m), 1965 (w), 1456 (m), 1060 (m), 713 cmÀ1 (w); MS
(EI): m/z (%): 138 (6) [MÀH2O]+, 110 (15), 95 (44), 81 (66), 67 (100), 55
(76).
(Z)-5-decen-2-one [(Z)-16]:[24] Yield: 125 mg (0.81 mmol, 81%). Rf =0.3
(petroleum ether/ethyl acetate 5:1); 1H NMR (300 MHz, CDCl3): d=
5.44–5.24 (m, 2H), 2.51–2.43 (m, 2H), 2.35–2.23 (m, 2H), 2.14 (s, 3H),
2.09–1.95 (m, 2H), 1.38–1.23 (m, 4H), 0.94–0.8 ppm (m, 3H); 13C NMR
(75 MHz, CDCl3): d=208.6, 131.3, 127.6, 43.7, 31.8, 30.0, 26.9, 22.4, 21.7,
14.0 ppm; IR (film): n˜ =2957 (m), 2926 (m), 2858 (w), 1966 (m), 1715 (s),
1359 (m), 1160 (m), 1014 (w), 795 cmÀ1 (m); MS (EI): m/z (%): 154 (9)
[M]+, 136 (4), 125 (12), 111 (22), 96 (69), 81 (100), 67 (58), 54 (81).
(Z)-4-Decene [(Z)-17]:[25] Yield: 135 mg (0.96 mmol, 96%). Rf =0.95
(pentane); 1H NMR (300 MHz, CDCl3): d=5.37–5.22 (m, 2H), 2.04–1.84
(m, 4H), 1.37–1.12 (m, 8H), 0.90–0.77 ppm (m, 6H); 13C NMR (75 MHz,
CDCl3): d=130.1, 129.6, 31.6, 29.5, 29.4, 27.3, 23.0, 22.6, 14.1, 13.9 ppm;
IR (film): n˜ =2945 (w), 2928 (m), 2895 (w), 1465 (w), 903 (s), 724 cmÀ1
(s); MS (EI): m/z (%): 140 (100) [M]+, 125 (5), 111 (16), 97 (52), 83 (75),
69 (45), 55 (28).
(Z)-3-Decene [(Z)-18]:[26] Yield: 133 mg (0.95 mmol, 96%). Rf =0.95
(pentane); 1H NMR (300 MHz, CDCl3): d=5.37–5.19 (m, 2H), 2.04–1.84
(m, 4H), 1.34–1.12 (m, 8H), 0.88 (t, J=7.5 Hz, 3H), 0.81 ppm (t, J=
6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3): d=131.5, 129.4, 31.8, 29.8, 29.0,
27.1, 22.7, 20.6, 14.4, 14.1 ppm; IR (film): n˜ =2959 (m,), 2924 (s), 2855
(m), 1459 (w), 1210 (w), 906 (s), 730 cmÀ1 (s); MS (EI): m/z (%): 140
(21) [M]+, 111 (6), 97 (15), 83 (13), 69 (45), 55 (100).
52.2 ppm; IR (film): n˜ =2956 (w), 1722 (s), 1437 (m), 1389 (m), 1215 (m),
1157 (s), 990 (w), 817 cmÀ1 (m); MS (EI): m/z (%): 144 (3) [M]+, 113
(100), 85 (20), 59 (27).
Dimethyl fumarate (22):[30] Rf =0.50 (petroleum ether/ethyl acetate 5:1);
1H NMR (300 MHz, CDCl3): d=6.88 (s, 2H), 3.82 ppm (s, 6H);
13C NMR (75 MHz, CDCl3): d=165.4, 133.4, 52.3 ppm; IR (film): n˜ =
2963 (w), 1710 (s), 1437 (m), 1302 (m), 1155 (m), 987 (s), 880 cmÀ1 (m);
MS (EI): m/z (%): 144 (3) [M]+, 113 (100), 85 (70), 59 (36), 53 (23).
(Z)-1,4-bis-Benzoyl-2-butene [(Z)-23]:[31] Yield: 284 mg (0.96 mmol,
96%). Rf =0.35 (petroleum ether/ethyl acetate 10:1); 1H NMR
(300 MHz, CDCl3): d=8.13–8.00 (m, 4H), 7.62–7.38 (m, 6H), 6.02–5.89
(m, 2H), 5.06–4.99 ppm (m, 4H); 13C NMR (75 MHz, CDCl3): d=166.4,
133.1, 129.9, 129.7, 128.4, 128.3, 60.6 ppm; IR (film): n˜ =1720 (s), 1266
(s), 1097 (m), 709 cmÀ1 (m); MS (EI): m/z (%): 296 (1) [M]+, 175 (5),
105 (100), 77 (29).
(Z)-1,4-bis-Formyl-2-butene [(Z)-24]:[32] Yield: 131 mg (0.91 mmol,
91%). Rf =0.5 (petroleum ether/ethyl acetate 2:1); 1H NMR (300 MHz,
CDCl3): d=7.97 (s, 2H), 5.77–5.65 (m, 2H), 4.70 ppm (d, J=4.9 Hz,
4H); 13C NMR (75 MHz, CDCl3): d=160.7, 127.9, 59.4 ppm; IR (film):
n˜ =2977 (m), 2864 (s), 1716 (s), 1120 (s), 934 (s), 845 cmÀ1 (s); MS (EI):
m/z (%): 98 (6) [MÀCO2]+, 70 (100), 57 (26).
Acknowledgements
(Z)-2-Decene [(Z)-19]:[27] Yield: 135 mg (0.96 mmol, 96%). Rf =0.95
(pentane); 1H NMR (300 MHz, CDCl3): d=5.44–5.26 (m, 2H), 2.05–1.91
(m, 4H), 1.56–1.52 (m, 3H), 1.32–1.13 (m, 8H), 0.88–0.72 ppm (m, 5H);
13C NMR (75 MHz, CDCl3): d=130.9, 123.6, 31.9, 29.6, 29.3, 29.2, 26.9,
22.7, 14.0, 12.7 ppm; IR (film): n˜ =2957 (m,), 2925 (s), 2855 (m), 1464
(w), 1377 (w), 907 (m), 732 cmÀ1 (m); MS (EI): m/z (%): 140 (22) [M]+,
111 (7), 97 (16), 83 (15), 69 (54), 55 (100).
(Z)-1-Phenyl-1-propene [(Z)-20]:[28] Yield: 111 mg (0.94 mmol, 94%).
Rf =0.90 (pentane); 1H NMR (300 MHz, CDCl3): d=7.34–7.06 (m, 5H),
6.37 (dq, J=11.6, 1.8 Hz, 1H), 5.72 (dq, J=11.6, 7.2 Hz, 1H), 1.83 ppm
(dd, J=7.2, 1.8 Hz, 3H); 13C NMR (75 MHz, CDCl3): d=137.7, 129.9,
128.8, 128.1, 126.8, 126.4, 14.6 ppm; IR (film): n˜ =3020 (m), 2937 (w),
1494 (m), 1443 (m), 962 (w), 912 (w), 764 (m), 692 cmÀ1 (s); MS (EI):
m/z (%): 117 (100) [MÀH]+, 103 (11), 91 (40), 77 (11), 63 (13), 51 (17).
(Z)-1-Formyl-5-decene [(Z)-21]: Yield: 168 mg (0.91 mmol, 91%). Rf =
0.75 (petroleum ether/ethyl acetate 10:1); 1H NMR (300 MHz, CDCl3):
d=7.99 (s, 1H), 5.43–5.19 (m, 2H), 4.15–4.05 (m, 2H), 2.08–1.84 (m,
4H), 1.71–1.51 (m, 2H), 1.43–1.14 (m, 6H), 0.90–0.77 ppm (m, 3H);
13C NMR (75 MHz, CDCl3): d=160.1, 129.7, 127.8, 62.9, 30.9, 27.1, 25.9,
25.6, 24.9, 21.3, 13.0 ppm; IR (film): n˜ =2927 (m), 2859 (w), 1728 (s),
1465 (w), 1165 cmÀ1 (s); MS (EI): m/z (%): 184 (1) [M]+, 138 (44), 110
(44), 95 (70), 81 (74), 67 (100), 55 (82), 41 (77), 29 (28); HRMS (ESI+
HR) calcd for C11H20O2: 184.1463; found: 184.1432.
(Z)-Methyl cinnamate [(Z)-21]:[29] Yield: 115 mg (0.71 mmol, 71%). Rf =
0.40 (petroleum ether/ethyl acetate 10:1); 1H NMR (300 MHz, CDCl3):
d=7.54–7.49 (m, 2H), 7.35–7.24 (m, 3H), 6.89 (d, J=12.4 Hz, 1H), 5.89
(d, J=12.4 Hz, 1H), 3.64 ppm (s, 3H); 13C NMR (75 MHz, CDCl3): d=
166.6, 143.4, 134.8, 129.7, 129.1, 128.1, 119.3, 51.4 ppm; IR (film): n˜ =2950
(w), 1723 (s), 1631 (m), 1436 (m), 1198 (s), 1167 (s), 827 (m), 696 cmÀ1
(m); MS (EI): m/z (%): 163 (36) [MÀH]+, 131 (100), 121 (6), 103 (10),
77 (4), 51 (2).
Financial support by the Fonds der Chemischen Industrie, the Deutsche
Forschungsgemeinschaft (SFB 706), Landesgraduiertenfçrderung Baden-
Wꢀrttemberg (PhD grant for C.B.) ,and the Dr-Otto-Rçhm-Gedꢁchtnis-
stiftung is gratefully acknowledged.
[1] For an excellent review on the Wittig olefination, see:B. E. Maryan-
[3] For a general review on the semireduction of alkynes, see: I. J. Mun-
slow in Modern Reduction Methods (Eds.: P. G. Andersson, I. J.
Munslow), Wiley-VCH, Weinheim, 2008, p. 363.
[4] Metal/NH3: a) L. Brandsma, W. F. Nieuwenhuizen, J. W. Zwikker,
U. Maeorg, Eur. J. Org. Chem. 1999, 5; b) K. K. Chan, N. Cohen,
[5] Metal hydrides: a) T. Tsuda, T. Yoshida, T. Kawamoto, T. J. Saegusa,
ganic Syntheses, Vol. 7, Wiley, New York, 1985, p. 524.
[7] Enzyme-catalyzed: A. Mꢀller, R. Stꢀrmer, B. Hauer, B. Rosche,
[8] a) J. W. Sprengers, J. Wassenaar, N. D. Clement, K. J. Cavell, C. J.
2005, 44, 2026; b) K. R. Campos, D. Cai, M. Journet, J. J. Kowal,
g) B. M. Choudary, G. V. M. Sharma, P. Bharath, Angew. Chem.
Savoia, E. Tagliavini, C. Trombini, A. Umani-Ronchi, J. Org. Chem.
(E)-Methyl cinnamate [(E)-21]:[29] Rf =0.40 (petroleum ether/ethyl ace-
tate 10:1); 1H NMR (300 MHz, CDCl3): d=7.63 (d, J=16.1 Hz, 1H),
7.49–7.42 (m, 2H), 7.35–7.29 (m, 3H), 6.37 (d, J=16.1 Hz, 1H), 3.74 ppm
(s, 3H); 13C NMR (75 MHz, CDCl3): d=167.4, 144.9, 134.4, 130.3, 128.9,
128.1, 117.8, 51.7 ppm; IR (film): n˜ =2950 (w), 1723 (s), 1631 (m), 1436
(m), 1198 (s), 1167 (s), 827 (m), 696 cmÀ1 (m); MS (EI): m/z (%): 163
(84) [MÀH]+, 131 (100), 121 (16), 103 (22), 77 (11), 51 (7).
Dimethyl maleate (22):[30] Yield: 33 mg (0.23 mmol, 23%). Rf =0.40 (pe-
1
troleum ether/ethyl acetate 5:1); H NMR (300 MHz, CDCl3): d=6.28 (s,
2H), 3.82 ppm (s, 6H); 13C NMR (75 MHz, CDCl3): d=165.7, 129.8,
Chem. Eur. J. 2010, 16, 12214 – 12220
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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