T. Sugimura et al. / Tetrahedron: Asymmetry 14 (2003) 881–890
889
(c 0.99, CH2Cl2); IR (neat) 1750, 1720 and 1650 cm−1;
1H NMR l 5.11 (m, 1H), 4.37 (t, J=3.5 Hz, 1H), 4.10
(m, 1H), 3.40 (s, 2H), 2.35–2.21 (m, 5H), 1.98–1.94 (m,
2H), 1.86–1.75 (m, 4H), 1.26 (d, J=6.1 Hz, 3H), 1.24
(d, J=6.1 Hz, 3H); MS m/z (M+) calcd for C14H22O4,
254.1518, obsvd 254.1521. 16C: colorless oil (77.3%
yield); [h]2D0=−42.8 (c 1.02, CH2Cl2); IR (neat) 1750,
4.09 (m, 1H), 2.21–2.15 (m, 2H), 2.05–1.98 (m, 2H),
1.76–1.65 (m, 4H), 1.55–1.39 (m, 4H), 1.27 (d, J=6.1
Hz, 3H), 1.18 (d, J=6.1 Hz, 3H); MS m/z (M+−N2)
calcd for C15H24O3, 252.1725, obsvd 252.1696. 18: yel-
low oil (45.6% yield); [h]2D0=−57.9 (c 1.05, CH2Cl2); IR
1
(neat) 2109 and 1695 cm−1; H NMR l 5.10 (m, 1H),
4.69 (s, 1H), 4.13 (m, 1H), 3.85 (d, J=1.6 Hz, 1H), 3.78
(d, J=1.6 Hz, 1H), 1.83–1.71 (m, 2H), 1.77 (s, 3H),
1.27 (d, J=6.4, 3H), 1.22 (d, J=6.1 Hz, 3H); 13C NMR
l 166.3, 158.1, 81.5, 68.9, 68.7, 46.2, 43.1, 21.3, 20.7.
19.3; MS m/z (M+−N2) calcd for C10H16O3, 212.1161,
obsvd 212.1158. 19: yellow oil (26.6% yield); [h]2D0=
−19.3 (c 1.06, CH2Cl2); IR (neat) 2100 and 1690 cm−1;
1H NMR l 7.58 (ddm, J=8.3, 1.5 Hz, 2H), 7.32 (m,
3H), 5.21 (m, 1H), 4.67 (s, 1H), 4.66 (d, J=2.7 Hz, 1H),
4.35 (m, 1H), 4.19 (d, J=2.7 Hz, 1H), 1.98 (ddd,
J=14.4, 8.3, 4.2 Hz, 1H), 1.88 (ddd, J=14.4, 8.8, 4.2
Hz, 1H), 1.32 (d, J=5.9 Hz, 3H), 1.31 (d, J=6.4 Hz,
3H); 13C NMR l 160.3, 158.3, 137.0, 128.3, 125.6, 69.5,
69.0, 46.2, 43.1, 20.4, 19.4; MS m/z (M+−N2) calcd for
C15H18O3, 246.1256, obsvd 246.1222.
1
1730 and 1660 cm−1; H NMR l 5.11 (m, 1H), 4.69 (t,
J=6.8 Hz, 1H), 3.98 (m, 1H), 3.40 (s, 2H), 2.26 (s, 3H),
2.20–2.17 (m, 2H), 2.04–1.99 (m, 2H), 1.78–1.40 (m,
8H), 1.26 (d, J=6.4 Hz, 3H), 1.24 (d, J=6.1 Hz, 3H);
MS m/z (M+) calcd for C16H26O4, 282.1832, obsvd
282.1876. 17C: colorless oil (90.0% yield); [h]2D0=−40.1
(c 1.04, CH2Cl2); IR (neat) 1750, 1720 and 1660 cm−1;
1H NMR l 5.09 (m, 1H), 4.44 (t, J=8.0 Hz, 1H), 4.10
(m, 1H), 3.40 (s, 2H), 2.42–2.39 (m, 2H), 2.25 (s, 3H),
2.16 (t, J=6.1 Hz, 1H), 2.05–2.04 (m, 2H), 1.87 (m,
1H), 1.77–1.17 (m, 8H), 1.27 (d, J=6.1 Hz, 3H), 1.17
(d, J=6.1 Hz, 3H); MS m/z (M+) calcd for C17H28O4,
296.1988, obsvd 296.2013. 18C: colorless oil (18.5%
yield); [h]2D0=−35.0 (c 0.51, CH2Cl2); IR (neat) 1740,
1
1720 and 1660 cm−1; H NMR l 5.15 (m, 1H), 4.14 (m,
1H), 3.85 (d, J=0.7 Hz, 1H), 3.79 (d, J=1.7 Hz, 1H),
3.40 (s, 2H), 2.25 (s, 3H), 1.79–1.55 (m, 5H), 1.26 (d,
J=6.4 Hz, 3H), 1.21 (d, J=5.9 Hz, 3H); 13C NMR l
2000.5, 166.5, 158.3, 81.6, 69.3, 68.5, 50.6, 43.0, 30.0,
21.3, 19.3; MS m/z (M+) calcd for C12H20O4, 228.1362,
obsvd 228.1320. 19C: colorless oil (84.6% yield); [h]2D01=
−51.0 (c 0.96, CH2Cl2); IR (neat) 1714, 1643 cm−1; H
NMR l 7.57 (m, 2H), 7.31 (m, 3H), 5.24 (m, 1H), 4.66
(d, J=2.7 Hz, 1H), 4.37 (m, 1H), 4.20 (d, J=2.7 Hz,
1H), 3.38 (s, 2H), 2.21 (s, 3H), 2.00–1.86 (m, 2H), 132
(d, J=6.1 Hz, 3H), 1.31 (d, J=6.4 Hz, 3H); 13C NMR
l 200.6, 166.5, 158.3, 137.0, 128.4, 128.1, 125.6, 83.3,
69.5, 69.2, 50.4, 43.0, 30.1, 20.5, 19.3; MS m/z (M+)
calcd for C17H22O4, 290.1518, obsvd 290.1559.
4.10. Metal-catalyzed reaction of 12–19 to give cyclo-
propanes 12D–19D
4.10.1. Intramolecular cycloaddition of 12–14. The diazo
ester substrate was dissolved in dichloromethane as a
ca. 1 M solution, and a catalytic amount of Rh2(OAc)4
was added at room temperature under stirring. After
30–60 min, the reaction mixture was concentrated and
purified by silica gel column chromatography (elution
with 10% ethyl acetate in hexane) to give cycloadduct
D. Stereochemistries of the major diastereomer were
determined by NOE experiments. Diastereomeric ratios
of 12D and 13D were determined by GLC after treat-
ments by ethanolysis and protection with TBS group
under the conditions converted 4 to 6. Diastereomeric
1
4.9.3. Conversion of 15C–19C to 15–19. To a solution of
C (1.5 g, 1.0 equiv.), p-toluenesulfonyl azide (1.5 equiv.)
in acetonitrile (30 ml), triethylamine (3.0 equiv.) was
added dropwise at 0°C. After stirring for 2–3 h, the
mixture was added to 1 M NaOH (15 ml). After 15–20
h of stirring, the mixture was extracted with diethyl
ether (50 ml, 3×) and washed with water (100 ml).
Drying over Na2SO4, concentration, and column chro-
matography on silica gel (elution with 20% ethyl acetate
in hexane) afforded 0.5–1.7 g of the diazo ester as a
deep yellow oil. 15: yellow oil (65.8% yield); [h]2D0=−
74.9 (c 1.04, CH2Cl2); IR (neat) 2110 and 1700 cm−1; 1H
NMR l 5.10 (m, 1H), 4.69 (s, 1H), 4.37 (s, 1H), 4.08
(m, 1H), 2.36–2.21 (m, 4H), 1.87–1.71 (m, 4H), 1.27 (d,
J=6.3 Hz, 3H), 1.24 (d, J=6.1 Hz, 3H); MS m/z
(M+−N2) calcd for C13H18O3, 210.1256, obsvd
210.1297. 16: yellow oil (71.2% yield); [h]2D0=−69.0 (c
ratio of 14D was determined by H NMR. 12D: mp
1
62–63°C; IR (KBr) 1730 cm−1; H NMR l 4.56 (ddd,
J=12.4, 12.4, 3.4 Hz, 1H, H-5), 4.13 (ddd, J=12.4, 6.2,
2.1 Hz, 1H, H-5%), 3.36 (dqd, J=12.4, 6.2, 2.1 Hz, 1H,
H-3), 2.09 (m, 1H), 2.03 (m, 1H), 1.97–1.85 (m, 2H),
1.77 (ddd, J=7.6, 7.6, 1.4 Hz, 1H, H-9), 1.70–1.59 (m,
2H), 1.55 (m, 1H), 1.34 (d, J=7.6 Hz, 1H, H-8),
1.33–1.26 (m, 2H), 1.12 (m, 1H), 1.13 (d, J=6.2 Hz,
1H); NOE enhancement between H-3 and H-9, 9%; 13C
NMR l 174.2, 65.2, 64.2, 63.5, 39.9, 91.9, 29.5, 23.0,
22.0, 21.3, 21.13, 21.09; HRMS m/z (M+) calcd for
C12H18O3, 210.1256, obsvd 210.1264; GLC after the
conversion (TC-1, 0.25 mm i.d.×25 m, 150°C, 29 cm/s)
retention times, 81.0 (major) and 83.0 min. 13D: mp
1
98.5–99.0°C; IR (KBr) 1711 cm−1; H NMR l 5.07 (m,
1H, H-5), 3.83 (ddd, J=13.1, 3.4, 3.4 Hz, 1H, H-3),
3.56 (m, 1H, H-3%), 2.28 (m, 1H), 2.23 (ddd, J=13.7,
5.5, 5.5 Hz, 1H), 2.03 (ddd, J=13.7, 13.7, 5.5 Hz, 1H),
1.88 (m, 1H), 1.66 (m, 1H), 1.56–1.42 (m, 2H), 1.48 (d,
J=6.2 Hz, 1H, H-8), 1.32 (d, J=6.2 Hz, 3H), 1.26–1.22
(m, 2H), 1.08 (m, 1H); NOE enhancement between H5
and H-8, 1.5%; 13C NMR l 177.0, 76.4, 71.2, 65.8, 40.9,
33.3, 29.6, 28.8, 23.6, 21.8, 20.9, 20.8; HRMS m/z (M+)
calcd for C12H18O3, 210.1256, obsvd 210.1264; GLC
after the conversion (TC-1, 0.25 mm i.d.×25 m, 150°C,
1
1.03, CH2Cl2); IR (neat) 2120 and 1700 cm−1; H NMR
l 5.09 (m, 1H), 4.70 (t, J=6.8 Hz, 1H), 4.68 (s, 1H),
4.00 (m, 1H), 2.21–2.18 (m, 2H), 2.03 (dd, J=11.0, 6.8
Hz, 1H), 1.80–1.60 (m, 4H), 1.55–1.39 (m, 4H), 1.26 (d,
J=6.4 Hz, 3H), 1.17 (d, J=6.1 Hz, 3H); MS m/z
(M+−N2) calcd for C14H22O3, 238.1569, obsvd
238.1602. 17: yellow oil (66.0% yield); [h]2D0=−71.4 (c
1
1.01, CH2Cl2); IR (neat) 2120 and 1700 cm−1; H NMR
l 5.09 (m, 1H), 4.69 (s, 1H), 4.44 (t, J=8.3 Hz, 1H),
29 cm/s) retention time, 84.2 min. 14D (as a