10816
G. Deng et al. / Tetrahedron 61 (2005) 10811–10817
85, 67, 55, 43, 41, 29. Anal. Calcd for C13H16N2O5: C,
55.71; H, 5.75; N, 9.99. Found: C, 55.69; H, 5.81; N, 10.10.
1034 cmK1; EIMS (m/z) 216 [(MKN2)C], 170 (100), 143,
131, 127, 115, 103, 89, 77, 65, 63, 52, 29. Anal. Calcd for
C13H12N2O3: C, 63.93; H, 4.95; N, 11.47. Found: C, 63.88;
H, 4.87; N, 11.49.
3.6. Typical procedure for the catalytic hydrogenation of
12b–e
3.7. Typical procedure for the Rh2(OAc)4-catalyzed
reaction of 8a–d
3.6.1. Ethyl 2-diazo-3-oxoundec-4-enoate (8a). To a
solution of 12b (250 mg, 1 mmol) in hexane (10 mL) was
added Lindlar catalyst (30 mg), and the reaction mixture
was stirred vigorously for 1 h at room temperature under
hydrogen gas balloon. The precipitate was filtrated and then
the solvent was removed in vacuo. The residue was purified
by chromatography (petroleum ether/Et2O 8:1) to give 8a
(244 mg, 97%) as yellow oil. 1H NMR (CDCl3, 300 MHz) d
6.93 (dt, JZ11.4, 1.5 Hz, 1H), 6.18 (dt, JZ11.4, 7.2 Hz,
1H), 4.25 (q, JZ7.1 Hz, 2H), 2.66–2.58 (m, 2H), 1.61–1.53
(m, 2H), 1.32–1.22 (m, 6H), 1.30 (t, JZ7.1 Hz, 3H), 0.83 (t,
JZ6.6 Hz, 3H); 13C NMR (CDCl3, 75 MHz) d 182.5, 161.3,
150.2, 123.4, 77.2, 31.6, 30.0, 29.1, 29.0, 28.0, 22.5, 14.3,
14.0; IR (KBr, cmK1) 2954, 2924, 2854, 2131, 1720, 1647,
1614, 1464, 1369, 1302, 1221, 1134, 1043; EIMS (m/z) 252
[MC], 226, 224, 205, 195, 178, 167, 150, 139, 121 (100),
108, 94, 81, 69, 55, 43, 41, 28. Anal. Calcd for C13H20N2O3:
C, 61.88; H, 7.99; N, 11.10. Found: C, 61.93; H, 7.89; N,
11.16.
3.7.1. Ethyl 2-cyclopente-1-one-4-pentyl-5-carboxylate
(14a). To
a
suspension of Rh2(OAc)4 (5.1 mg,
0.0115 mmol) in anhydrous CH2Cl2 (10 mL) at room
temperature was added 8a (290 mg, 1.15 mmol) in
anhydrous CH2Cl2 (5 mL) over 5 min. After stirring for
another 12 h, the reaction mixture was concentrated in
vacuo. The residue was chromatographed on silica
(petroleum ether/Et2O 6:1) to give 14a (228 mg, 88%) as
1
colorless oil. H NMR (CDCl3, 300 MHz) d 7.64 (dd, JZ
5.7, 2.4 Hz, 1H), 6.07 (dd, JZ5.7, 2.1 Hz, 1H), 4.17 (q, JZ
7.2 Hz, 2H), 3.26–3.22 (m, 1H), 2.96 (d, JZ3.0 Hz, 1H),
1.63–1.54 (m, 2H), 1.49–1.22 (m, 6H), 1.24 (t, JZ7.2 Hz,
3H), 0.84 (t, JZ7.1 Hz, 3H); 13C NMR (CDCl3, 75 MHz) d
202.5, 169.0, 168.0, 131.5, 61.4, 58.0, 46.0, 33.8, 31.5, 27.0,
22.3, 14.1, 13.8; IR (KBr, cmK1) 2958, 2929, 2858, 1739,
1712, 1589, 1466, 1369, 1255, 1146, 1024; EIMS (m/z) 225
[(MCH)C], 179 (100), 151, 123, 109, 95, 81, 67. Anal.
Calcd for C13H20O3: C, 69.61; H, 8.99. Found: C, 69.55; H,
9.01.
3.6.2. Ethyl 2-diazo-3-oxotridec-4-enoate (8b). A yellow
oil was obtained in 95% yield. 1H NMR (CDCl3, 300 MHz)
d 6.93 (dt, JZ11.4, 1.8 Hz, 1H), 6.17 (dt, JZ11.4, 7.5 Hz,
1H), 4.25 (q, JZ7.1 Hz, 2H), 2.65–2.57 (m, 2H), 1.43–1.36
(m, 2H), 1.21–1.32 (m, 10H), 1.28 (t, JZ7.1 Hz, 3H), 0.83
(t, JZ6.6 Hz, 3H); 13C NMR (CDCl3, 75 MHz) d 182.5,
161.3, 150.1, 123.4, 77.2, 61.3, 31.8, 30.0, 29.6, 29.3, 29.2,
28.1, 22.6, 14.3, 14.0; IR (KBr, cmK1) 2958, 2927, 2856,
2133, 1718, 1647, 1612, 1464, 1369, 1304, 1219, 1134,
1041; EIMS (m/z) 280 [MC], 254, 252, 223, 206, 195, 178,
167, 156, 149, 135, 121, 108, 94, 81, 67, 55, 43, 41, 29
(100). Anal. Calcd for C15H24N2O3: C, 64.26; H, 8.63; N,
9.99. Found: C, 64.31; H, 8.70; N, 9.90.
3.7.2. Ethyl 2-cyclopente-4-heptyl-1-one-5-carboxylate
(14b). A colorless oil was obtained in 86% yield. 1H
NMR (CDCl3, 300 MHz) d 7.63 (dd, JZ5.7, 2.7 Hz, 1H),
6.06 (dd, JZ5.7, 2.3 Hz, 1H), 4.16 (q, JZ7.1 Hz, 2H),
3.25–3.21 (m, 1H), 2.95 (d, JZ2.7 Hz, 1H), 1.62–1.53 (m,
2H), 1.47–1.21 (m, 10H), 1.23 (t, JZ7.1 Hz, 3H), 0.82 (t,
JZ7.1 Hz, 3H); 13C NMR (CDCl3, 75 MHz) d 202.5, 168.9,
167.9, 131.5, 61.4, 58.0, 46.0, 33.9, 31.6, 29.3, 29.0, 27.3,
22.5, 14.1, 13.9; IR (KBr, cmK1) 2958, 2929, 2856, 1739,
1709, 1591, 1466, 1369, 1252, 1146, 1032; EIMS (m/z) 253
[(MCH)C], 225, 207, 179 (100), 151, 123, 109, 95, 81, 67.
Anal. Calcd for C15H24O3: C, 71.39; H, 9.59. Found: C,
71.35; H, 9.64.
3.6.3. Ethyl 2-diazo-3-oxo-6-(tetrahydro-2H-pyran-2-
yloxy)hex-4-enoate (8c). A yellow oil was obtained in
94% yield. 1H NMR (CDCl3, 300 MHz) d 7.06 (dt, JZ11.7,
2.4 Hz, 1H), 6.39 (dt, JZ11.7, 4.8 Hz, 1H), 4.76–4.74 (m,
1H), 4.65–4.63 (m, 1H), 4.59–4.57 (m, 1H), 4.25 (q, JZ
7.2 Hz, 2H), 3.84–3.78 (m, 1H), 3.49–3.42 (m, 1H), 1.85–
1.67 (m, 2H), 1.57–1.49 (m, 4H), 1.28 (t, JZ7.2 Hz, 3H);
13C NMR (CDCl3, 75 MHz) d 182.0, 161.1, 148.2, 122.4,
98.8, 77.2, 66.9, 62.4, 61.5, 30.6, 25.4, 19.6, 14.3; IR (KBr,
cmK1) 2943, 2871, 2360, 2133, 1718, 1647, 1606, 1419,
1371, 1306, 1211, 1122, 1030, 968, 910 cmK1; EIMS (m/z)
264 [(MKN2)C], 198, 181, 155, 141, 124, 109, 97, 85
(100), 67, 57, 43, 41, 29. Anal. Calcd for C13H18N2O5: C,
55.31; H, 6.43; N, 9.92. Found: C, 55.40; H, 6.49; N, 9.83.
3.7.3. Ethyl 2-cyclopente-1-one-4-(tetrahydro-2H-pyran-
2-yloxy)-5-carboxylate (14c). A colorless oil was obtained
1
in 82% yield. H NMR (CDCl3, 300 MHz) d 7.58 (dd, JZ
6.0, 2.4 Hz, 1H), 6.19 (dd, JZ6.0, 2.7 Hz, 1H), 5.21 (m,
1H), 4.75–4.73 (m, 1H), 4.22 (q, JZ7.1 Hz, 2H), 3.89–3.74
(m, 1H), 3.54–3.46 (m, 1H), 3.43 (d, JZ3.0 Hz, 1H), 1.77–
1.71 (m, 2H), 1.52–1.51 (m, 4H), 1.27 (t, JZ7.1 Hz, 3H);
13C NMR (CDCl3, 75 MHz) d 199.0, 168.1, 162.4, 133.4,
100.3, 79.5, 63.2, 61.5, 59.2, 30.6, 25.2, 19.7, 14.2; IR (KBr,
cmK1) 2945, 2873, 1741, 1716, 1595, 1444, 1369, 1346,
1261, 1146, 1024, 906 cmK1; EIMS (m/z) 254 [MC], 225,
207, 179 (100), 151, 123, 107, 95, 81, 67, 55. Anal. Calcd
for C13H18O5: C, 61.40; H, 7.14. Found: C, 61.32; H, 7.25.
3.6.4. Ethyl 2-diazo-3-oxo-5-phenylpent-4-enoate (8d). A
yellow oil was obtained in 92% yield. H NMR (CDCl3,
1
3.7.4. Ethyl 2-hydroxy-1-naphthoate (15). A colorless oil
was obtained in 65% yield. H NMR (CDCl3, 300 MHz) d
1
300 MHz) d 7.62–7.59 (m, 2H), 7.32–7.30 (m, 3H), 6.91 (d,
JZ12.6 Hz, 1H), 6.86 (d, JZ12.7 Hz, 1H), 4.27 (q, JZ
7.2 Hz, 2H), 1.30 (t, JZ7.2 Hz, 3H); 13C NMR (CDCl3,
75 MHz) d 182.5, 161.0, 141.6, 135.0, 129.8, 129.2, 128.0,
124.1, 77.2, 61.4, 14.2; IR (KBr) 2958, 2925, 2854, 2360,
2343, 2131, 1712, 1637, 1603, 1369, 1302, 1217, 1130,
12.08 (s, 1H), 8.40 (d, JZ8.4 Hz, 1H), 7.77 (d, JZ8.7 Hz,
1H), 7.74–7.33 (m, 3H), 7.26 (d, JZ8.7 Hz, 1H), 4.45 (q,
JZ7.2 Hz, 2H), 1.44 (t, JZ7.2 Hz, 3H); IR (KBr, cmK1
2954, 2925, 2854, 1649, 1579, 1466, 1398, 1375, 1381,
1255, 1207, 1161, 1092, 829, 796, 773.
)