A R T I C L E S
Shimizu et al.
Complex 17. Dark brown crystals. IR (KBr): 3047, 2934, 2856,
CHCl3)].3b IR (neat): 2962, 2905, 2866, 1763, 1477, 1439, 1371, 1288,
1236, 1155, 1059, 978, 880, 731 cm-1. 1H NMR (CDCl3): δ 4.36 (dd,
J ) 9.5, 6.3 Hz, 1H), 4.24 (dd, J ) 9.5, 1.5 Hz, 1H), 3.19 (m, 1H),
3.10 (m, 1H), 2.56 (m, 1H), 2.41 (m, 1H), 2.21-2.07. 13C NMR
(CDCl3): δ 180.5, 74.0, 38.1, 34.4, 25.4, 23.6. Anal. Calcd for
C6H8O2: C, 64.27; H, 7.19. Found: C, 64.30; H, 7.14.
3.3.5. (1S,2RS,5R)-2-Hydroxy-3-oxabicyclo[3.3.0]octane (13c).
Colorless oil (78% yield). Compound 13c was a single diastereomer,
although the configuration of C2 has not been determined. IR (neat):
3402, 2949, 1447, 1335, 1049, 1007, 962, 908 cm-1 1H NMR
.
1
1821, 1614, 1578, 1425, 1319, 1105, 1026, 814, 746, 700 cm-1. H
NMR (CDCl3): δ 8.28 (br s, 1H), 8.22 (br s, 1H), 8.13 (d, J ) 8.3 Hz,
1H), 7.95 (d, J ) 8.3 Hz, 1H), 7.92 (d, J ) 8.1 Hz, 1H), 7.87 (s, 1H),
7.79 (s, 1H), 7.74 (d, J ) 7.8 Hz, 1H), 7.65 (d, J ) 7.8 Hz, 1H), 7.62
(d, J ) 8.3 Hz, 1H), 7.56 (d, J ) 8.1 Hz, 1H), 7.37 (br d, J ) 8.1 Hz,
2H), 7.31-6.98 (m, 27H), 6.92 (m, 3H), 6.81 (d, J ) 8.5 Hz, 1H),
6.60 (dq, J ) 8.3 Hz, 4H), 6.53 (d, J ) 8.1 Hz, 2H), 6.20 (d, J ) 8.1
Hz, 2H), 4.04 (br t, J ) 11.2 Hz, 1H), 3.03 (br t, J ) 11.2 Hz, 1H),
2.59 (m, 2H), 2.00 (br d, J ) 11.2 Hz, 1H), 1.91 (br d, J ) 11.2 Hz,
1H), 1.66 (m, 1H), 1.41 (m, 1H), 1.26 (m, 2H), 0.96 and 0.90 (each s,
9H). HRMS (FAB) m/z 1467.4492 ([M]+ calcd for C92H80ClN3O3-
RuSi2+: 1467.4470).
(CDCl3): δ 5.22 (s, 1H), 4.19 (dd, J ) 8.8, 7.3 Hz, 1H), 3.64 (dd, J )
8.8, 2.5 Hz, 1H), 2.82-2.74 (m, 1H), 2.59 (dt, J ) 8.8, 4.9 Hz, 1H),
2.46 (d, J ) 2.2 Hz, 1H), 1.84-1.76 (m, 2H), 1.65-1.40 (m, 4H). 13
C
NMR (CDCl3): δ 104.7, 73.7, 51.3, 42.3, 33.9, 30.9, 26.5. Anal. Calcd
for C7H12O2: C, 65.60; H, 9.44. Found: C, 65.73; H, 9.47. HRMS
(EI) m/z 129.0905 ([M + H]+ calcd for C7H13O2: 129.0916).
3.3.6. (1S,5R)-3-Oxabicyclo[3.3.0]octan-2-one (14c). Colorless oil
Complex 18. Red brown crystals. IR (KBr): 3547, 3047, 2934, 2856,
1807, 1643, 1614, 1580, 1425, 1321, 1105, 1026, 814, 746, 700 cm-1
.
1H NMR (CDCl3): δ 8.22 (br d, J ) 11.5 Hz, 2H), 8.15 (d, J ) 8.3
Hz, 1H), 8.11 (d, J ) 8.3 Hz, 1H), 7.95 (d, J ) 7.8 Hz, 1H), 7.86 (m,
3H), 7.65 (t, J ) 8.5 Hz, 2H), 7.49 (t, J ) 8.5 Hz, 2H), 7.32-6.87 (m,
31H), 6.82 (t, J ) 7.1 Hz, 1H), 6.44 (br t, J ) 7.3 Hz, 4H), 6.19 (d,
J ) 7.3 Hz, 4H), 3.76 (br t, J ) 11.5 Hz, 1H), 3.09 (br t, J ) 11.5 Hz,
1H), 2.70 (br d, J ) 11.5 Hz, 1H), 2.57 (br d, J ) 11.5 Hz, 1H), 2.04
(m, 2H), 1.80 (m, 1H), 1.63-1.39 (m, 3H), 0.91 and 0.88 (each s,
9H). HRMS (FAB) m/z 1449.4835 ([M]+ calcd for C92H81N3O4-
RuSi2+: 1449.4809).
(66% ee). [R]23 +66.5 (c 0.95, CHCl3) [lit.: [R]D +96.9 (c 1,
25
D
CHCl3)].3b IR (neat): 2959, 2910, 2870, 1763, 1481, 1450, 1331, 1263,
1184, 1140, 1101, 1061, 1011, 970, 934, 901, 841, 708 cm-1. 1H NMR
(CDCl3): δ 4.47 (dd, J ) 9.5, 7.8 Hz, 1H), 3.99 (dd, J ) 9.5, 3.4 Hz,
1H), 3.01 (dt, J ) 9.3, 2.4 Hz, 1H), 2.95 (m, 1H), 2.10 (m, 1H), 1.91
(m, 2H), 1.73 (m, 1H), 1.65-1.52 (m, 2H). 13C NMR (CDCl3): δ 180.7,
73.6, 53.5, 44.5, 39.1, 33.9, 30.8, 25.6. Anal. Calcd for C7H10O2: C,
66.65; H, 7.99. Found: C, 66.65; H, 8.08.
3.3. Syntheses of Optically Active Lactols and Lactones. 3.3.1.
(1R,6S,7RS)-7-Hydroxy-8-oxabicyclo[4.3.0]nonane (13a). meso-Diol
12a (14.4 mg, 0.1 mmol) and complex 10 (4.6 mg, 4.0 µmol, 4 mol
%) were dissolved in anhydrous CHCl3 (0.5 mL). The solution was
stirred at ambient temperature under irradiation with a halogen lamp
in air for 7 days. The mixture was directly chromatographed on silica
gel (n-hexane/ethyl acetate ) 1/1) to give the corresponding lactol 13a
(11.4 mg, 80%) as a colorless oil. Compound 13a was a >95:<5
mixture of isomers diastereomeric at C7. IR (neat): 3383, 2928, 1448,
3.3.7. (1S*,7R*,8RS)-8-Hydroxy-9-oxabicyclo[5.3.0]decane (13d).
The product was obtained as a 3:1 mixture of isomers diastereomeric
at C8. Absolute configuration of the product has not been determined.
Colorless oil (80% yield). IR (neat): 3358, 2916, 2851, 1456, 1339,
1248, 1092, 997, 930, 878 cm-1 1H NMR of the major isomer
.
(CDCl3): δ 5.10 (t, J ) 2.9 Hz, 1H), 4.22 (t, J ) 8.4 Hz, 1H), 3.52
(dd, J ) 8.4, 5.9 Hz, 1H), 2.66 (d, J ) 2.9 Hz, 1H), 2.63-2.53 (m,
1H), 2.19 (ddt, J ) 12, 9.0, 2.9 Hz, 1H), 1.94-1.70 (m, 5H), 1.60-
1.18 (m, 5H). 1H NMR of the minor isomer (CDCl3): δ 5.35 (m, 1H),
4.09 (t, J ) 8.5 Hz, 1H), 3.62 (t, J ) 8.5 Hz, 1H), 2.47 (d, J ) 2.9 Hz,
1H, -OH), 2.32 (m, 2H), 1.92-1.15 (m, 10H). 13C NMR of the major
isomer (CDCl3): δ 105.6, 73.9, 51.3, 41.5, 31.4, 30.6, 29.0, 28.5, 28.2.
13C NMR of the minor isomer (CDCl3): δ 100.1, 72.7, 48.1, 41.9,
31.5, 30.2, 30.0, 28.1, 25.2. HRMS (EI) m/z 155.1072. Found for
diastereomeric mixture ([M - H]+ calcd for C9H15O2: 155.1072).
3.3.8. (1S*,7R*)-9-Oxabicyclo[5.3.0]decan-8-one (14d). Colorless
oil (63% ee). Absolute configuration of the product has not been
determined. [R]24D +38.3 (c 0.35, CHCl3). IR (neat): 2924, 2853, 1763,
1
1047, 997, 908 cm-1. H NMR (CDCl3): δ 5.17 (s, 1H), 4.05 (t, J )
8.0 Hz, 1H), 3.72 (t, J ) 8.0 Hz, 1H), 2.63 (d, J ) 3.2 Hz, 1H), 2.60-
2.50 (m, 1H), 2.08-2.01 (m, 1H), 1.70-1.52 (m, 4H), 1.46-1.38 (m,
2H), 136-1.24 (m, 2H). 13C NMR (CDCl3): δ 102.6, 70.5, 44.9, 35.0,
24.3, 24.1, 23.4, 21.9. Anal. Calcd for C8H14O2: C, 67.57; H, 9.92.
Found: C, 67.50; H, 9.96.
3.3.2. (1R,6S)-8-Oxabicyclo[4.3.0]nonan-7-one (14a). To a suspen-
sion of the lactol 13a (11.4 mg, 0.08 mmol) and molecular sieves 4A
(120 mg) in anhydrous CH2Cl2 (0.5 mL) was added pyridinium
dichromate (60 mg, 0.16 mmol). The mixture was stirred overnight at
room temperature, diluted with n-hexane/ethyl acetate (4/1), and filtered
through a pad of silica gel. The filtrate was concentrated under reduced
pressure. The enantiomeric excess of the resulting lactone 14a was
determined to be 80% ee by GLC analysis. [R]23D +40.4 (c 0.21, CHCl3)
[lit.: [R]25D +48.8 (c 0.5, CHCl3)].3b IR (neat): 2934, 2856, 1773, 1448,
1375, 1348, 1319, 1275, 1211, 1188, 1161, 1128, 1067, 1040, 986,
939, 914, 849, 712 cm-1. 1H NMR (CDCl3): δ 4.20 (dd, J ) 8.8, 5.1
Hz, 1H), 3.96 (dd, J ) 8.8, 1.2 Hz, 1H), 2.64 (dt, J ) 6.3, 3.2 Hz,
1H), 2.49-2.43 (m, 1H), 2.13 (br d, J ) 12 Hz, 1H), 1.85-1.78 (m,
1H), 1.67-1.58 (m, 3H), 1.30-1.18 (m, 3H). 13C NMR (CDCl3): δ
178.0, 71.7, 39.6, 35.5, 27.3, 23.6, 23.1, 22.7. HRMS (EI) m/z 140.0841
([M]+ calcd for C8H12O2: 140.0837).
3.3.3. (1S,2RS,5R)-2-Hydroxy-3-oxabicyclo[3.2.0]heptane (13b).
Colorless oil (64% yield). Compound 13b was a single diastereomer,
although the configuration of C2 has not been determined. IR (neat):
3395, 2936, 1292, 1074, 966, 910 cm-1. 1H NMR (CDCl3): δ 5.35 (s,
1H), 4.04 (dd, J ) 9.0, 5.6 Hz, 1H), 3.84 (d, J ) 9.0 Hz, 1H), 3.02-
2.95 (m, 1H), 2.92-2.86 (m, 1H), 2.55 (br s, 1H), 2.24-2.06 (m, 2H),
1.74-1.64 (m, 2H). 13C NMR (CDCl3): δ 102.9, 73.0, 44.7, 36.6, 23.6,
20.4. Anal. Calcd for C6H10O2: C, 63.14; H, 8.83. Found: C, 62.96;
H, 8.84.
1481, 1458, 1383, 1281, 1169, 1030, 993, 912, 876, 808, 700 cm-1
.
1H NMR (CDCl3): δ 4.39 (dd, J ) 9.3, 7.8 Hz, 1H), 3.90 (dd, J )
9.3, 5.4 Hz, 1H), 2.79 (dt, J ) 9.8, 4.4 Hz, 1H), 2.72 (m, 1H), 2.06
(m, 1H), 1.94-1.72 (m, 4H), 1.69-1.48 (m, 2H), 1.40-1.25 (m, 3H).
13C NMR (CDCl3): δ 179.9, 73.0, 44.3, 40.0, 31.3, 31.0, 28.2, 28.1,
27.52. HRMS (EI) m/z 154.1003 ([M]+ calcd for C9H14O2+: 154.0994).
3.3.9. (1R,6S,7RS)-7-Hydroxy-8-oxabicyclo[4.3.0]non-3-ene (13e).
Compound 13e was a single diastereomer, although the configuration
of C7 has not been determined. Colorless oil (68% yield). IR (neat):
1
3387, 3024, 2889, 1719, 1659, 1437, 1256, 1213, 988, 891 cm-1. H
NMR (CDCl3): δ 5.68 (m, 2H), 5.17 (s, 1H), 4.13 (t, J ) 8.0 Hz, 1H),
3.59 (t, J ) 8.0 Hz, 1H), 2.98 (d, J ) 3.2 Hz, 1H), 2.69 (m, 1H),
2.36-2.18 (m, 3H), 1.98-1.86 (m, 2H). 13C NMR (CDCl3): δ 124.6,
124.5, 103.5, 72.3, 41.5, 32.9, 23.3, 23.1. HRMS (EI) m/z 140.0842
([M]+ calcd for C8H12O2+: 140.0837).
3.3.10. (1R,6S)-8-Oxabicyclo[4.3.0]non-3-en-7-one (14e). Colorless
oil (75% ee). [R]20D -58.9 (c 0.30, acetone) [lit.: [R]20D -85.4 (c 2.63,
acetone)].3f IR (neat): 3030, 2970, 2905, 2843, 1763, 1659, 1479, 1437,
1373, 1308, 1225, 1198, 1175, 1134, 1080, 1042, 1013, 995, 978, 945,
1
895, 800, 731, 706, 665 cm-1. H NMR (CDCl3): δ 5.75 (d, J ) 2.4
Hz, 2H), 4.32 (dd, J ) 8.8, 5.1 Hz, 1H), 4.03 (dd, J ) 8.8, 2.2 Hz,
1H), 2.79 (dt, J ) 8.1, 2.7 Hz, 1H), 2.63 (dddd, J ) 15.6, 7.3, 5.1, 2.2
Hz, 1H), 2.52 (br d, J ) 17.3 Hz, 1H), 2.43-2.34 (m, 1H), 2.31-2.24
3.3.4. (1S,5R)-3-Oxabicyclo[3.2.0]heptan-2-one (14b). Colorless oil
(74% ee). [R]23 +88.0 (c 0.22, CHCl3) [lit.: [R]25 +118.7 (c 10,
D
D
9
5410 J. AM. CHEM. SOC. VOL. 127, NO. 15, 2005