C. Y. Im, T. Okuyama, T. Sugimura
FULL PAPER
of the TBS group starting with 1.01 g of the substrate gave
216.40, 166.53, 152.28, 126.44, 123.04, 122.12, 115.90, 88.17, 62.96,
32.07, 30.90, 29.69, 26.90, 21.39 ppm. HRMS (ESI): calcd. for
C14H16NaO5 [M + Na]+ 287.0895; found 287.0937. Ether 16: Yield:
626.9 mg of the deprotected product (88.9%). IR (NaCl, neat): ν
˜
= 3446, 2979, 1717, 1699, 1695, 1683, 1674, 1652, 1635, 1616, 1575,
1
1557, 1505, 1456, 1419, 746 cm–1. H NMR (CDCl3, 600 MHz): δ 38%. Colorless oil. IR (NaCl, neat): ν = 2979, 1747, 1597, 1496,
˜
1
= 6.91 (dd, J = 8.2, 2.1 Hz, 1 H), 6.87–6.79 (m, 3 H), 5.83 (br. s, 1
H, OH), 5.25 (td, J = 12.4, 6.2 Hz, 1 H), 4.12–4.05 (m, 2 H), 3.44
(s, 2 H), 2.22 (s, 3 H), 2.08–2.04 (m, 2 H), 1.32 (d, J = 6.2 Hz, 3
H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 223.84, 166.75, 145.59,
1260, 756 cm–1. H NMR (CDCl3, 600 MHz): δ = 7.14–7.07 (m, 4
H), 6.96 (m, 1 H), 5.40–5.35 (m, 2 H), 4.69 (s, 1 H, assigned to S),
4.48 (s, 1 H, R), 4.44 (ddd, J = 10.0, 5.5, 2.4 Hz, 1 H, S), 4.39 (ddd,
J = 11.0, 5.5, 2.7 Hz, 1 H, R), 4.29 (td, J = 11.0, 2.1 Hz, 1 H, R),
121.89, 120.09, 114.96, 112.28, 69.20, 65.19, 50.32, 35.48, 30.13, 3.99 (td, J = 10.0, 1.4 Hz, 1 H, S), 2.48 (s, 3 H, R), 2.46 (s, 3 H,
20.36, 20.19, 19.96 ppm. HRMS (ESI): calcd. for C14H18NaO5 [M
S), 2.07–1.98 (m, 2 H), 1.95–1.89 (m, 2 H), 1.32 (d, J = 6.2 Hz, 3
+ Na]+ 289.1052; found 289.1072. Formation of the diazo group
H, S), 1.26 (d, J = 6.2 Hz, 3 H, R) ppm. 13C NMR (CDCl3,
with 557 mg of this substrate gave 595.3 mg of 13 (92.6%). IR 150 MHz): δ = 203.30, 201.24, 166.85, 166.68, 150.57, 148.00,
(NaCl, neat): ν = 3446, 2979, 2146, 1739, 1716, 1700, 1695, 1683, 125.90, 125.54, 123.33, 122.72, 122.59, 122.33, 118, 40, 115.70,
˜
1675, 1652, 1616, 1575, 1505, 1456, 1419, 744 cm–1. 1H NMR 89.06, 87.02, 71.90, 71.32, 70.27, 67.28, 34.37, 31.98, 30.89, 26.82,
(CDCl3, 600 MHz): δ = 6.92 (dd, J = 7.6, 1.4 Hz, 1 H), 6.88–6.79
(m, 3 H), 5.80 (d, J = 2.1 Hz, 1 H, OH), 5.37 (td, J = 12.4, 6.2 Hz,
1 H), 4.11 (td, J = 9.6, 6.2 Hz, 1 H), 4.05 (dt, J = 9.6, 6.2 Hz, 1
H), 2.44 (s, 3 H), 2.11 (q, J = 6.2 Hz, 2 H), 1.38 (d, J = 6.2 Hz, 3
H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 189.95, 161.16, 146.11,
145.47, 122.07, 120.09, 115.12, 112.30, 76.37, 69.45, 65.14, 35.70,
28.23, 20.49 ppm. HRMS (ESI): calcd. for C14H16N2NaO5 [M +
Na]+ 315.0957; found 315.0909.
26.69, 20.19 ppm. HRMS (ESI): calcd. for C14H16NaO5 [M +
Na]+ 287.0895; found 287.0908.
Preparation of 17a and 17b: LiAlH4 (2.2 mg, 1.5 mol) was added to
a stirred solution of 9 (10 mg) in diethyl ether (3 mL) at –78 °C.
After stirring for 2 h, the mixture was treated with water at –78 °C.
This mixture was warmed to room temperature, extracted with di-
ethyl ether, and washed with water and then brine. Drying with
Na2SO4, concentration, and column chromatography on silica gel
(elution with 40% ethyl acetate in hexane) afforded 17a (77% yield
as a diastereomeric ratio (73:27). IR of the isomeric mixture: IR
General Procedure for Decomposition of the Diazo Compounds: An-
alytical runs: Rh2(L)4 (5 mol-%) was added to a solution of a diazo
substrate in CDCl3 (0.7 mL) at room temperature. After stirring at
(NaCl, neat): ν = 3497, 2976, 2932, 1734, 1595, 1496, 1451, 1378,
˜
1
room temperature for 2 h, the crude mixture was analyzed by H
1257, 1197, 1175, 1109, 1084, 1039, 956, 758 cm–1. Major isomer:
1H NMR (CDCl3, 600 MHz): δ = 7.02 (dt, J = 16.5, 7.6 Hz, 2 H),
6.97 (dd, J = 7.6, 1.4 Hz, 1 H), 6.93 (td, J = 7.6, 1.4 Hz, 1 H), 5.16
NMR spectroscopy. Synthetic runs: A CH2Cl2 (10–30 mL) solution
of the substrate was added dropwise to a solution of Rh2(OC-
OC3F7)4 (5 mol-%) in CH2Cl2 (10–20 mL) at room temperature. (m, 1 H), 4.32 (m, 1 H), 4.24 (m, 1 H), 3.90 (d, J = 8.9 Hz, 1 H),
After stirring at room temperature for 2 h, the solution was concen-
trated under vacuum. The residue was purified by silica gel
chromatography (elution with 30% ethyl acetate in hexane). Ether
9: Yield: 76%. M.p. 108–110 °C. [α]2D0 = +201.75 (c = 0.63,
2.91 (br. s, 1 H), 2.28 (dt, J = 15.1, 11.0 Hz, 1 H), 1.62 (d, J =
15.1 Hz, 1 H), 1.52 (d, J = 6.2 Hz, 3 H), 1.32 (d, J = 6.2 Hz, 3 H),
1.21 (d, J = 6.2 Hz, 3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ =
168.84, 153.13, 147.49, 126.29, 123.42, 122.51, 116.46, 91.68, 79.74,
CH Cl ). IR (NaCl, neat): ν = 2978, 2934, 1739, 1596, 1496, 1452, 72.08, 66.71, 42.97, 23.34, 21.01, 17.18 ppm. HRMS (ESI): calcd.
˜
2
2
1417, 1380, 1357, 1258, 1193, 1109, 1084, 994, 945, 912, 818,
for C15H20NaO5 [M + Na]+ 303.1208; found 303.1149. Minor iso-
754 cm–1. 1H NMR (CDCl3, 600 MHz): δ = 7.10–7.07 (m, 2 H), mer: H NMR (CDCl3, 600 MHz): δ = 7.02 (dt, J = 16.5, 7.6 Hz,
1
6.97 (dd, J = 8.2, 1.4 Hz, 1 H), 6.93 (td, J = 7.6, 1.4 Hz, 1 H), 5.17
2 H), 6.95–6.89 (m, 2 H), 5.09 (m, 1 H), 4.32 (m, 1 H), 4.24 (m, 1
(m, 1 H), 4.58 (s, 1 H), 4.24 (m, 1 H), 2.47 (s, 3 H), 2.23 (dt, J = H), 3.89 (d, J = 7.6 Hz, 1 H), 2.35 (dt, J = 15.1, 11.0 Hz, 1 H),
15.1, 11.0 Hz, 1 H), 1.61 (dt, J = 15.1, 1.4 Hz, 1 H), 1.51 (d, J = 1.60 (d, J = 15.1 Hz, 1 H), 1.51 (d, J = 6.2 Hz, 3 H), 1.45 (d, J =
6.2 Hz, 3 H), 1.30 (d, J = 6.2 Hz, 3 H) ppm. 13C NMR (CDCl3,
150 MHz): δ = 201.84, 166.14, 153.02, 146.78, 126.59, 123.01,
122.38, 116.24, 90.23, 79.33, 72.57, 42.97, 26.65, 23.23, 20.83 ppm.
HRMS (ESI): calcd. for C15H18NaO5 [M + Na]+ 301.1052; found
301.1055. Ether 14: Yield: 63% yield. M.p. 120–122 °C. [α]2D0 = +2.2
6.2 Hz, 3 H), 1.37 (d, J = 6.2 Hz, 3 H) ppm. 13C NMR (CDCl3,
150 MHz): δ = 169.41, 153.13, 147.85, 126.08, 123.35, 122.35,
116.40, 90.00, 79.74, 72.63, 67.12, 42.63, 23.30, 21.10, 19.71 ppm.
(S)- or (R)-MTPACl (10 μL) and DMAP (ca. 10 mg) were added
to a solution of 17a (5 mg) in CH3CN (2 mL) at room temperature.
(c = 0.50, CH Cl ). IR (NaCl, neat): ν = 2981, 2934, 1734, 1652, After stirring for 1 h, the mixture was quenched with a 2 m HCl
˜
2
2
1596, 1498, 1456, 1419, 1360, 1260, 1081, 941, 912, 826, 806, 752,
aqueous solution. This mixture was extracted with diethyl ether
667 cm–1. 1H NMR (CDCl3, 600 MHz): δ = 7.13 (td, J = 8.2, and washed with the HCl solution, water, and then brine. Drying
1.4 Hz, 1 H), 7.07 (dd, J = 7.9, 1.4 Hz, 1 H), 6.99 (dd, J = 8.2,
1.4 Hz, 1 H), 6.91 (td, J = 7.9, 1.4 Hz, 1 H), 5.40 (ddd, J = 12.4,
6.5, 3.4 Hz, 1 H), 4.72 (ddd, J = 12.4, 6.5, 2.7 Hz, 1 H), 4.21 (s, 1
H), 2.50 (s, 3 H), 1.98 (ddd, J = 15.4, 6.5, 3.4 Hz, 1 H), 1.86 (ddd,
J = 15.4, 6.5, 2.7 Hz, 1 H), 1.52 (d, J = 6.5 Hz, 3 H), 1.20 (d, J =
with Na2SO4 and concentration afforded (R)-17b when the (S) rea-
gent was employed and (S)-17b when the (R) reagent was em-
ployed. (R)-17b: 1H NMR (CDCl3, 600 MHz): δ = 7.57 (dt, J =
25.4, 4.8 Hz, 2 H), 7.42 (dd, J = 5.8, 2.1 Hz, 2 H), 7.34 (d, J =
2.1 Hz, 1 H), 7.01 (dd, J = 7.6, 1.0 Hz, 1 H), 6.92 (dd, J = 8.2,
6.5 Hz, 3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 203.87, 1.4 Hz, 1 H), 6.79 (td, J = 7.6, 1.0 Hz, 1 H), 6.56 (dd, J = 8.2,
166.34, 151.93, 148.39, 126.29, 123.14, 121.83, 115.15, 87.44, 72.71,
68.27, 36.75, 26.98, 20.72, 20.02 ppm. HRMS (ESI): calcd. for
C15H18NaO5 [M + Na]+ 301.1052; found 301.1046. Ether 15: Yield:
1.4 Hz, 1 H), 5.73 (m, 1 H), 5.19 (m, 1 H), 4.22 (m, 1 H), 4.11 (d,
J = 9.3 Hz, 1 H), 3.59 (s, 3 H), 2.38–2.27 (m, 1 H), 1.61 (dt, J =
15.8, 1.4 Hz, 1 H), 1.51 (d, J = 6.5 Hz, 3 H), 1.36 (d, J = 6.9 Hz,
54%. Colorless oil. IR (NaCl, neat): ν = 2925, 1744, 1596, 1496,
3 H), 1.34 (d, J = 6.5 Hz, 3 H) ppm. HRMS (ESI): calcd. for
˜
1
1
1453, 1259, 928, 758 cm–1. H NMR (CDCl3, 600 MHz): δ = 7.12 C25H27F3NaO7 [M + Na]+ 519.1607; found 519.1660. (S)-17b: H
(td, J = 8.2, 1.4 Hz, 1 H), 7.08 (dd, J = 7.9, 1.7 Hz, 1 H), 6.99 (dd,
J = 8.2, 1.4 Hz, 1 H), 6.92 (td, J = 7.9, 1.4 Hz, 1 H), 4.76 (dtd, J
= 11.3, 4.8, 1.4 Hz, 1 H), 4.54 (m, 1 H), 4.40 (s, 1 H), 4.09 (tt, J =
NMR (CDCl3, 600 MHz): δ = 7.64 (d, J = 7.6 Hz, 2 H), 7.48 (d,
J = 6.9 Hz, 1 H), 7.35–7.32 (m, 2 H), 7.08–7.08 (m, 2 H), 6.98–
6.93 (m, 2 H), 5.71 (m, 1 H), 5.24 (m, 1 H), 4.25 (m, 1 H), 4.18 (d,
11.3, 1.4 Hz, 1 H), 2.50 (s, 3 H), 2.15 (m, 1 H), 1.85 (m, 1 H), 1.53 J = 7.6 Hz, 1 H), 3.60 (s, 3 H), 2.31 (m, 1 H), 1.63 (dt, J = 15.1,
(d, J = 6.2 Hz, 3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ =
1.4 Hz, 1 H), 1.53 (d, J = 6.2 Hz, 3 H), 1.34 (d, J = 6.2 Hz, 3 H),
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Eur. J. Org. Chem. 2008, 285–294