H. Murakami et al. / Journal of Organometallic Chemistry 691 (2006) 3151–3156
3155
product purified by silica gel column chromatography
(CH2Cl2) to give 2-vinyl-2,3-dihydrofuran derivatives (4)
as listed in Table 2.
d 38.7, 82.5, 111.8, 117.2, 127.6, 128.6, 128.9, 129.4,
129.9, 130.0, 131.1, 136.6, 165.6, 193.5. IR (neat): m 3060,
1610, 1574, 1491, 1446, 1367, 1238, 1115, 992, 927, 886,
696 cmꢀ1. HRMS calc. for C19H16O2: 276.1150. Found:
276.1145.
2-Vinyl-4-acetyl-5-methyl-2,3-dihydrofuran (4a) [14c]:
1
pale yellow oil. H NMR (CDCl3, 20 ꢁC): d 2.18 (s, 3H),
2.21 (dd, J = 1.5 and 1.5 Hz, 3H), 2.73 (ddd, J = 14.1,
8.0 and 1.5 Hz, 1H), 3.12 (ddd, J = 14.1, 10.5 and 1.5 Hz,
1H), 5.02 (ddddd, J = 10.5, 8.0, 6.6, 1.2 and 0.9 Hz, 1H),
5.22 (ddd, J = 10.2, 1.2 and 0.9 Hz, 1H), 5.30 (ddd,
J = 17.4, 0.9 and 0.9 Hz, 1H), 5.92 (ddd, J = 17.4, 10.2
and 6.6 Hz, 1H). 13C{1H} NMR (CDCl3, 20 ꢁC): d 15.0,
29.4, 36.3, 82.6, 111.9, 116.9, 136.6, 167.3, 194.4. IR (neat):
1,1,6,6-Tetrabenzoyl-3-hexene (6): white powder. 1H
NMR (CDCl3, 20 ꢁC):
d 2.74 (m, 4H), 5.16 (t,
J = 6.6 Hz, 2H), 5.57–5.62 (m, 2H), 7.42 (ddd, J = 8.4,
7.5 and 1.8 Hz, 8H), 7.55 (tt, J = 7.5 and 1.8 Hz, 4H),
7.88 (ddd, J = 8.4, 1.8 and 1.2 Hz, 8H). 13C{1H} NMR
(CDCl3, 20 ꢁC): d 32.3, 56.8, 128.5, 128.9, 129.7, 133.5,
135.8, 195.5. IR (KBr): m 3038, 3031, 2963, 2917, 1685,
m 2989, 2928, 1715, 1671, 1599, 1227, 989, 934, 625 cmꢀ1
.
1667, 1596, 1448, 1357, 1342, 1180, 1007, 924, 701 cmꢀ1
HRMS calc. for C34H28O4: 500.1988. Found: 500.1979.
.
HRMS. calc. for C9H12O2: 152.0837. Found: 152.0832.
2-Vinyl-4-ethoxycarbonyl-5-methyl-2,3-dihydrofuran (4b)
1
[15]: pale yellow oil. H NMR (CDCl3, 20 ꢁC): d 1.27 (t,
3.4. Cyclodehydration of cis–2-butene-1,4-diol (2) with
1,3-cyclohexanedione (3f)
J = 7.1 Hz, 3H), 2.20 (dd, J = 1.5 and 1.5 Hz, 3H), 2.67
(ddd, J = 14.1, 8.0 and 1.5 Hz, 1H), 3.06 (ddd, J = 14.1,
10.5 and 1.5 Hz, 1H), 4.15 (q, J = 7.1 Hz, 2H), 5.02
(ddddd, J = 10.5, 8.0, 6.6, 1.2 and 0.9 Hz, 1H), 5.24 (ddd,
J = 10.2, 1.2 and 0.9 Hz, 1H), 5.30 (ddd, J = 17.4, 0.9
and 0.9 Hz, 1H), 5.92 (ddd, J = 17.4, 10.2 and 6.6 Hz,
1H). 13C{1H} NMR (CDCl3, 20 ꢁC): d 14.1, 14.4, 35.6,
59.5, 82.5, 101.7, 116.6, 136.9, 166.1, 167.5. IR (neat): m
2982, 2871, 1704, 1651, 1257, 1224, 1082, 990, 968,
762 cmꢀ1. HRMS. calc. for C10H14O3: 182.0943. Found:
182.0939.
The reaction of Eq. (2) was conducted similarly to Sec-
tion 3.3, using 2 (43.85 mg, 0.50 mmol), 3f (111.94 mg,
1.00 mmol), 1 (11.1 mg, 0.010 mmol), pyridine (10.81 mg,
0.10 mmol), and THF (1 mL) as the solvent. The reaction
mixture was stirred for 0.5 h under reflux, quenched with
Et3N (0.1 mL), and purified by silica gel column chroma-
tography (hexane:AcOEt = 4:1 and then 2:1) to afford 4f
as a pale yellow oily material (34 mg, 42%). 1H NMR
(CDCl3, 20 ꢁC): d 2.04 (qui, J = 6.3 Hz, 2H), 2.35 (t,
J = 6.3 Hz, 2H), 2.44 (ddt, J = 6.3, 1.2 and 1.2 Hz, 2H),
2.61 (ddt, J = 14.4, 7.5 and 1.2 Hz, 1H), 3.01 (ddt,
J = 14.4, 10.2 and 1.2 Hz, 1H), 5.15–5.24 (m, 1H), 5.24
(ddd, J = 10.5, 1.2 and 0.9 Hz, 1H), 5.32 (ddd, J = 17.1,
1.2 and 1.2 Hz, 1H), 5.93 (ddd, J = 17.1, 10.5 and 6.6 Hz,
1H). 13C{1H} NMR (CDCl3, 20 ꢁC): d 21.6, 23.9, 31.8,
36.4, 85.7, 112.9, 117.4, 136.2, 177.1, 195.5. IR (neat): m
2952, 2896, 2827, 2252, 1624, 1403, 1230, 987, 909,
649 cmꢀ1. HRMS calc. for C10H12O2: 164.0829. Found:
164.0837.
2-Vinyl-4-benzoyl-5-methyl-2,3-dihydrofuran (4ca) [16]:
pale yellow oil. 1H NMR (CDCl3, 20 ꢁC): d 1.83 (t,
J = 1.5 Hz, 3H), 2.90 (ddd, J = 14.4, 8.3 and 1.5 Hz, 1H),
3.24 (ddd, J = 14.4, 10.1 and 1.5 Hz, 1H), 5.09 (ddddd,
J = 10.5, 8.0, 6.6, 1.2 and 0.9 Hz, 1H), 5.24 (ddd,
J = 10.2, 1.2 and 0.9 Hz, 1H), 5.30 (ddd, J = 17.4, 0.9
and 0.9 Hz, 1H), 5.92 (ddd, J = 17.4, 10.2 and 6.6 Hz,
1H), 7.35–7.60 (m, 5H). 13C{1H} NMR (CDCl3, 20 ꢁC):
d 15.4, 36.9, 82.6, 112.2, 117.0, 127.7, 128.2, 129.1, 130.9,
136.5, 168.4, 193.0. IR (neat): m 2926, 1718, 1623, 1591,
1239, 1117, 1071, 989, 918, 699 cmꢀ1. HRMS calc. for
C14H14O2: 214.0994. Found: 214.0989.
References
2-Vinyl-4-acetyl-5-phenyl-2,3-dihydrofuran (4cb): pale
1
yellow oil. H NMR (CDCl3, 20 ꢁC): d 1.96 (s, 3H), 2.94
[1] (a) J. Tsuji, Transition Metal Reagents and Catalysts, Wiley, New
York, 2000;
(dd, J = 14.8 and 8.2 Hz, 1H), 3.30 (dd, J = 14.8 and
10.3 Hz, 1H), 5.10–5.20 (m, 1H), 5.26 (ddd, J = 10.4, 1.3
and 0.9 Hz, 1H), 5.38 (ddd, J = 16.9, 0.9 and 0.9 Hz,
1H), 6.00 (ddd, J = 17.0, 10.4 and 6.6 Hz, 1H), 7.40–7.60
(m, 5H). 13C{1H} NMR (CDCl3, 20 ꢁC): d 28.8, 37.1,
82.6, 114.5, 117.1, 128.3, 129.2, 130.6, 130.8, 136.6, 194.6.
IR (neat): m 2924, 1717, 1608, 1386, 1222, 1102, 975, 901,
703 cmꢀ1. HRMS calc. for C14H14O2: 214.0994. Found:
214.0999.
(b) J.A. Davis, in: E.W. Able, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 9, Pergamon Press,
Oxford, 1995, p. 291;
(c) S.A. Godleski, in: B.M. Trost, I. Fleming (Eds.), Comprehensive
Organic Synthesis, vol. 3, Pergamon Press, New York, 1991, p. 585.
[2] (a) B.M. Trost, Angew. Chem. Int. Ed. 34 (1995) 259;
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(b) Y. Kayaki, T. Koda, T. Ikariya, Eur. J. Org. Chem. (2004) 4989;
(c) N. Komine, A. Sako, S. Hirahara, M. Hirano, S. Komiya, Chem.
Lett. 34 (2005) 246;
(d) H. Bricout, J.-F. Carpentier, A.J. Mortreux, Mol. Catal. A 136
(1998) 243, and references cited therein.
2-Vinyl-4-benzoyl-5-phenyl-2,3-dihydrofuran (4d) [17]:
pale yellow oil. 1H NMR (CDCl3, 20 ꢁC): d 3.14 (dd,
J = 15.0 and 8.4 Hz, 1H), 3.45 (dd, J = 15.0 and 10.0 Hz,
1H), 5.25–5.27 (m, 1H), 5.31 (ddd, J = 11.5, 1.3 and
1.3 Hz, 1H), 5.46 (ddd, J = 17.0, 1.3 and 1.3 Hz, 1H),
6.10 (ddd, J = 17.4, 10.2 and 6.6 Hz, 1H), 7.00–7.50 (m,
5H), 7.00–7.50 (m, 5H). 13C{1H} NMR (CDCl3, 20 ꢁC):
[4] (a) T. Satoh, M. Ikeda, M. Miura, M. Nomura, J. Org. Chem. 62
(1997) 4877;
(b) S.-C. Yang, Y.-C. Tsai, Organometallics 20 (2001) 763;
´
(c) I. Stray, I.G. Stara, P. Kocovsky, Tetrahedron 50 (1994) 529;