K.-i. Yamada et al. / Tetrahedron 65 (2009) 903–908
907
FABMS m/z: 801 (MþNa). FABHRMS m/z: 801.4721 (calcd for
(CH2), 39.2 (CH2), 40.29 (C), 40.5 (C), 41.3 (CH2), 41.4 (CH2), 50.1
(CH), 50.3 (CH), 53.3 (CH), 64.78 (C), 76.69 (CH), 76.8 (CH), 81.9 (C),
82.15 (C), 99.1 (CH), 123.5 (CH), 125.3 (CH), 125.38 (CH), 125.6 (CH),
125.8 (CH), 125.9 (CH), 127.3 (CH), 127.89 (CH), 127.92 (CH), 128.01
(CH), 139.3 (C), 142.3 (C), 149.9 (C), 150.6 (C), 168.6 (C), 170.8 (C). 13C
NMR minor: 21.75 (CH3), 22.1 (CH3), 22.5 (CH3), 22.6 (CH3), 23.24
(CH3), 23.66 (CH3), 23.8 (CH3), 27.7 (CH2), 27.84 (CH2), 30.5 (CH3),
31.09 (CH3), 31.1 (CH), 31.27 (CH), 31.6 (CH3), 34.3 (CH2), 38.6 (CH2),
39.6 (CH2), 40.26 (C), 40.7 (C), 41.0 (CH2), 41.5 (CH2), 50.2 (CH), 50.6
(CH), 54.6 (CH), 64.76 (C), 76.73 (CH), 76.9 (CH), 81.8 (C), 82.20 (C),
98.8 (CH), 123.4 (CH), 125.1 (CH), 125.44 (CH), 125.7 (CH), 126.0
(CH), 127.6 (CH), 128.00 (CH), 128.1 (CH), 140.0 (C), 141.1 (C), 150.0
(C), 150.8 (C), 169.0 (C), 170.7 (C). IR (KBr): 2924, 1720, 1458, 1373,
1250, 1157, 1065, 972, 764, 702. FABMS m/z: 763 (MþH). FABHRMS
m/z: 763.4930 (calcd for C50H67O6: 763.4938).
C50H66O7Na: 801.4706).
4.3.3. Bis((1S,2R,5S)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl)
1-chloro-3-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)indane-2,2-
dicarboxylate (18)
To a solution of 17 (222 mg, 0.28 mmol) and triethylamine
(0.12 mL) in dry dichloromethane (1 mL) was added thionyl chlo-
ride (0.04 mL, 0.6 mmol) dropwise at 0 ꢁC. After stirring for 0.5 h at
0 ꢁC, the mixture was heated under reflux for 2 h. The mixture was
cooled to 0 ꢁC and poured into ice water. The aqueous layer was
extracted with chloroform, and the combined organic layers were
washed with brine, dried over Na2SO4, and concentrated to give
dark brown oil (276 mg), which was purified by column chroma-
tography (ethyl acetate/hexane 1/20) to give a 71/15/8/6 di-
25
astereoisomeric mixture of 18 (167 mg, 71%) as yellow solid of [a]
D
ꢀ25.2 (c 1.00, CHCl3). Rf¼0.50 (ethyl acetate/hexane 1/16). The di-
astereomeric ratio of 18 was determined by the integration area of
1H NMR signals at 6.08, 5.65, 6.10, and 5.72 ppm.
4.3.5. Methyl 1-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)indane-2-
carboxylate (20)
A mixture of 19 (84 mg, 0.11 mmol) and 4 M aq KOH (0.4 mL,
2 mmol) in DMSO (2 mL) was stirred at 140 ꢁC for 2 h, and then
diluted with 2 mL of ice water and 2 mL of diethyl ether. The
aqueous layer was extracted with diethyl ether, and the combined
organic layers were washed with brine, dried over Na2SO4, and
concentrated to give pale yellow oil. Silica gel column chromato-
1H NMR: 0.07 (s, 0.5H), 0.16 (s, 0.2H), 0.21 (s, 0.2H), 0.22 (s, 2.1H),
0.50–2.55 (m, 43H), 2.97 (d, J¼7.0, 0.15H), 3.24 (d, J¼2.8, 0.06H),
3.51 (d, J¼7.1, 0.08H), 3.95 (d, J¼2.8, 0.71H), 4.75–5.26 (m, 2H), 5.28
(d, J¼7.0, 0.15H), 5.35 (d, J¼2.8, 0.06H), 5.37 (d, J¼7.1, 0.08H), 5.65 (s,
0.15H), 5.72 (s, 0.06H), 5.78 (d, J¼2.8, 0.71H), 6.08 (s, 0.71H), 6.10 (s,
0.08H), 6.49–7.52 (m, 14H). 13C NMR, major isomer: 21.67 (CH3),
21.70 (CH3), 21.92 (CH3), 22.24 (CH3), 22.9 (CH3), 23.0 (CH3), 23.6
(CH3), 27.3 (CH2), 27.48 (CH2), 31.0 (CH3), 31.1 (CH3), 31.2 (CH), 31.4
(CH), 34.2 (CH2), 34.3 (CH2), 40.35 (C), 40.43 (C), 41.4 (CH2), 42.2
(CH2), 50.46 (CH), 50.50 (CH), 53.1 (CH), 64.5 (CH), 69.2 (C), 77.3
(CH), 77.5 (CH), 82.4 (C), 82.6 (C), 98.4 (CH), 124.0 (CH), 125.2 (CH),
125.3 (CH), 125.4 (CH), 125.71 (CH), 125.73 (CH), 125.8 (CH), 127.58
(CH), 127.87 (CH), 128.0 (CH), 138.7 (C), 141.4 (C), 150.3 (C), 150.53
(C), 167.5 (C), 168.7 (C); other isomers: 21.2 (CH3), 21.3 (CH3), 21.51
(CH3), 21.54 (CH3), 21.61 (CH3), 21.63 (CH3), 21.87 (CH3), 22.02
(CH3), 22.04 (CH3), 22.11 (CH3), 22.13 (CH3), 22.21 (CH3), 22.3 (CH3),
22.4 (CH3), 22.5 (CH3), 22.7 (CH3), 23.5 (CH3), 23.8 (CH3), 24.0 (CH3),
27.51 (CH2), 27.4 (CH2), 29.5 (CH2), 31.21 (CH), 31.30 (CH), 34.1
(CH2), 34.4 (CH2), 34.5 (CH2), 34.6 (CH2), 40.5 (C), 40.6 (C), 41.0
(CH2), 41.3 (CH2), 41.6 (CH2), 42.0 (CH2), 50.0 (CH), 50.1 (CH), 50.5
(CH), 50.9 (CH), 53.7 (CH), 66.0 (CH), 68.4 (C), 68.9 (C), 70.3 (C), 76.1
(CH), 77.2 (CH), 77.9 (CH), 81.7 (C), 82.2 (C), 100.8 (CH), 123.7 (CH),
125.0 (CH), 125.2 (CH), 125.5 (CH), 125.71 (CH), 127.64 (CH), 127.92
(CH), 137.7 (C), 139.9 (C), 140.0 (C), 150.50 (C), 150.6 (C), 151.1 (C),
165.5 (C),169.2 (C). IR (KBr): 2924,1737,1732,1258,1199,1163,1134,
1078, 759, 700. FABMS m/z: 797 (MþH). FABHRMS m/z: 797.4527
(calcd for C50H66O6Cl: 797.4548).
graphy (ethyl acetate/hexane 1/12) recovered L-8-phenylmenthol
(51 mg, quant) as colorless oil. In turn, the combined aqueous layers
were acidified with 10% HCl (2 mL) at 0 ꢁC and extracted with
diethyl ether. The combined organic layers were washed with
brine, dried over Na2SO4, and concentrated. The resulting crude oil
in benzene (3.5 mL) and MeOH (0.5 mL) was treated with 1 M
hexane solution of TMSCHN2 at room temperature. The mixture
was stirred until gas evolution ceased, and subsequently concen-
trated to give colorless oil (98.3 mg). Silica gel column chroma-
tography (ethyl acetate/hexane 1/10) gave 20 (26.7 mg, 80%) as
25
colorless oil of [
a
]
D
ꢀ46.1 (c 1.33, CHCl3). Rf¼0.31 (ethyl acetate/
hexane 1/15). 1H NMR: 1.18 (s, 3H), 1.19 (s, 3H), 1.20 (s, 3H), 1.21 (s,
3H), 3.15 (m,1H), 3.23–3.29 (m, 2H), 3.72 (s, 3H), 3.77 (dd, J¼6.1, 6.4,
1H), 5.11 (d, J¼6.4, 1H), 7.16–7.19 (m, 3H), 7.44 (m, 1H). 13C NMR:
22.2 (CH3), 22.3 (CH3), 23.9 (CH3), 24.1 (CH3), 36.0 (CH2), 45.4 (CH),
51.8 (CH3), 54.3 (CH), 81.9 (C), 82.4 (C), 102.2 (CH), 124.2 (CH), 125.7
(CH), 126.6 (CH), 127.4 (CH), 141.0 (C), 142.2 (C), 175.9 (C). IR (neat):
2982, 2951, 1738, 1442, 1369, 1221, 1163, 1134, 750. FABMS m/z: 305
(MþH). FABHRMS m/z: 305.1721 (calcd for C18H25O4: 305.1753).
4.3.6. Methyl 1-(hydroxymethyl)indane-2-carboxylate (21)
A mixture of 20 (26 mg, 0.08 mmol) and triethylsilane (0.08 mL,
0.8 mmol) in TFA (0.5 mL) was stirred under reflux for 1 h. The
mixture was cooled to room temperature and then concentrated to
give colorless oil (27.8 mg). Silica gel column chromatography
4.3.4. Bis((1S,2R,5S)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl)
1-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)indane-2,2-
dicarboxylate (19)
(ethyl acetate/hexane 1/12) gave 21 (20.6 mg, quant) as colorless oil
25
A
mixture of 18 (166 mg, 0.21 mmol), Bu3SnH (0.14 mL,
of [
a
]
D ꢀ39.2 (c 0.95, CHCl3). Rf¼0.33 (ethyl acetate/hexane 1/15).
0.5 mmol), and AIBN (7 mg, 0.03 mmol) in toluene (2 mL) was
stirred under reflux for 1 h. Concentration gave colorless oil, which
was purified by silica gel column chromatography to give an 83/17
1H NMR: 3.15 (ddd, J¼7.6, 8.0, 9.5, 1H), 3.26 (dd, J¼7.6, 16, 1H), 3.30
(dd, J¼9.5, 16, 1H), 3.75 (s, 3H), 3.98 (ddd, J¼5.5, 7.1, 7.6, 1H), 4.62
(dd, J¼7.1, 11, 1H), 4.69 (dd, J¼5.5, 11, 1H), 7.19–7.28 (m, 4H). 13C
NMR: 35.2 (CH2), 47.0 (CH), 47.1 (CH), 52.2 (CH3), 69.5 (CH2), 123.7
(CH), 124.8 (CH), 127.2 (CH), 128.1 (CH), 139.8 (C), 141.5 (C), 174.5 (C).
IR (neat): 3395, 2955, 1790, 1736, 1218, 1165, 756. FABMS m/z: 207
(MþH). FABHRMS m/z: 207.1062 (calcd for C12H15O3: 207.1021).
diastereoisomeric mixture of 19 (77.3 mg, 86%) as colorless solid of
25
mp 50–55 ꢁC and [
a
]
ꢀ19.4 (c 1.17, CHCl3). Rf¼0.55 (ethyl acetate/
D
hexane 1/16). The diastereomeric ratio of 19 was determined by the
integration area of 1H NMR signals at 3.64 and 3.84 ppm.
1H NMR, major: 0.47 (s, 3H), 0.65–2.17 (m, 43H), 3.37 (d, J¼16,
1H), 3.64 (d, J¼16,1H), 4.05 (d, J¼4.0,1H), 4.82 (m,1H), 4.98 (m,1H),
5.72 (d, J¼4.0, 1H), 7.07–7.38 (m, 14H); minor: 0.63 (s, 3H), 0.65–
2.23 (m, 43H), 3.32 (d, J¼16, 1H), 3.84 (d, J¼16, 1H), 4.07 (d, J¼4.6,
1H), 4.82 (m, 1H), 4.98 (m, 1H), 5.28 (d, J¼4.6, 1H), 7.07–7.38 (m,
14H). 13C NMR major: 21.7 (CH3), 21.79 (CH3), 22.3 (CH3), 22.7 (CH3),
23.18 (CH3), 23.35 (CH3), 23.38 (CH3), 23.69 (CH3), 27.4 (CH2), 27.75
(CH2), 30.8 (CH3), 30.9 (CH3), 31.13 (CH), 31.30 (CH), 34.2 (CH2), 34.4
Acknowledgements
This research was partially supported by the 21st Century Center
of Excellence Program ‘Knowledge Information Infrastructure for
Genome Science’ and a Grant-in-Aid for Young Scientist (B) from
JSPS, a Grant-in-Aid for Scientific Research on Priority Areas ‘Ad-
vanced Molecular Transformations’ from the Ministry of Education,