62
S. Nakano et al. / Tetrahedron: Asymmetry 12 (2001) 59–62
eluent to give cis-2-acetoxyindan-1-ol 6a (7.08 g, 74%)
as pale yellow needles. This was the authentic sample to
compare with the mixture of 6a and 6b. 6a: mp 101–
102°C; IR (KBr)=3310, 1740, 1260 cm−1; 1H NMR
(CDCl3, TMS): l=2.09 (3H, s, CH3), 2.29 (1H, br-d,
J=7.4 Hz, OH), 3.07 (1H, dd, J=16.8, 3.0 Hz, CH2),
3.21 (1H, dd, J=16.8, 5.5 Hz, CH2), 5.22 (1H, t, J=5.5
Hz, CH) 5.46 (1H, td, J=5.5, 3.0 Hz, CH), 7.22–7.48
(4H, m, arom.). When the pH was adjusted to more
than 10, cis-1,2-indandiol 5 was obtained in a 90% yield
from trans-2-bromo-1-indanol as off-white powder. 5:
mp 106–107°C; IR (KBr)=3367 cm−1; 1H NMR
(CDCl3, TMS): l=3.12 (1H, dd, J=16.1, 5.7 Hz,
CH2), 3.24 (1H, dd, J=16.1, 3.6 Hz, CH2), 4.74 (1H,
m, CH), 5.09 (2H, br-s, OH), 5.30 (1H, d, J=4.8 Hz,
CH), 7.21–7.71 (4H, m, arom.).
solution to form a slurry-like mixture. The mixture was
filtered and filtrate was washed with CH3CN (10 ml)
and dried in vacuo to give (1S,2R)-1-amino-2-indanol 1
(2.67 g, 77%, e.e.=96%), [h]D −60 (c 1.0, CHCl3), as a
white powder.
References
1. (a) Darke, P. L.; Huff, J. R. Adv. Pharmacol. 1994, 25, 399;
(b) Condra, J. H.; Shleif, W. A.; Blahy, O. M.; Gabryelski,
L. J.; Graham, D. J.; Quitero, J. C.; Rhodes, A.; Robbins,
H. L.; Roth, E.; Shivaprakash, M.; Titus, D.; Yang, T.;
Tepper, H.; Squires, K. E.; Deutsh, P. J.; Emili, E. A.
Nature 1995, 374, 569; (c) Holloway, M. K.; Jenny, M. W.;
Hargren, T. A.; Fitzgerald, P. M. D.; Vacca, J. P.; Dorsey,
B. D.; Levin, R. B.; Thompson, W. J.; Chen, L. J.; de
Solms, S. J.; Gaffin, N.; Lyle, T. A.; Sanders, W. M.;
Tucker, T. J.; Wiggins, M.; Wiscount, C. M.; Wolterdolf,
O. W.; Young, S. D.; Darck, P. L.; Zugay, J. A. J. Med.
Chem. 1994, 37, 3443 and references cited therein.
2. (a) Didier, E.; Loubinoux, B.; Ramos Tombo, G. M.; Rihs,
G. Tetrahedron 1991, 47, 4941; (b) Hong, Y.; Gao, Y.; Nie,
X.; Zepp, C. M. Tetrahedron Lett. 1994, 35, 6631; (c)
Davies, I. W.; Senanayake, C. H.; Larsen, R. D.; Verho-
even, T. R.; Reider, P. J. Tetrahedron Lett. 1996, 37, 813.
3. (a) Ghosh, A. K.; Chen, Y. Tetrahedron Lett. 1995, 36,
6811; (b) Ghosh, A. K.; Onishi, M. Tetrahedron: Asymme-
try 1996, 7, 375; (c) Zheng, N.; Armstrong, J. D.;
McWilliams, J. C.; Volante, R. P. Tetrahedron Lett. 1997,
38, 2817.
3.3. Lipase-catalyzed acetylation of cis-1,2-indandiol 5
A solution of 5 (1.51 g, 10 mmol) in the solvent of
choice (30 ml, Table 1) was treated with lipase PS (1.51
g) and vinyl acetate (0.86 g, 10 mmol) and the resulting
mixture was stirred at 35°C. The reaction was moni-
tored by HPLC and stopped by filtering off the enzyme.
The filtrate was concentrated under reduced pressure.
The evaporation residue was then subjected to silica gel
column chromatography (20 g, eluent: hexane/ethyl
acetate (2:1)) The enantiomeric purities of 6a and 7
were determined by their conversion to diols (10 mg of
sample and 1 g of 25% NaOH were stirred at 60°C for
0.5 hours, and the reaction mixture was extracted with
CH2Cl2 (10 ml)). After evaporation, 5 was obtained as
white powder). The regioisomeric ratio of 6a and 6b
4. (a) Jacobsen, E. N.; Zhang, W.; Mucci, A. R.; Ecker, J.
R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063; (b)
Jacobsen, E. N.; Larrow, F. J. J. Am. Chem. Soc. 1994, 116,
12129.
1
was determined by H NMR (CDCl3, TMS) spectra,
and the characteristic peak of the acetyl group CH3
protons was observed at l=2.09 for 6a and l=2.15 for
6b.
5. (a) Ogasawara, K.; Takahashi, M. Synthesis 1996, 954; (b)
Ghosh, A. K.; Kincaid, J. F.; Haske, M. G. Synthesis 1997,
541.
3.4. Preparative acetylation of 5
6. (a) Boyd, D. R.; Sharma, N. D.; Bowers, N. I.; Goodrich,
P. A.; Groocock, M. R.; Blacker, A. J.; Clarke, D. A.;
Howard, T.; Dalton, H. Tetrahedron: Asymmetry 1996, 7,
1559; (b) Igarashi, Y.; Otsutomo, S.; Harada, M.; Nakano,
S.; Watanabe, S. Synthesis 1997, 549; (c) Igarashi, Y.;
Otsutomo, S.; Harada, M.; Nakano, S. Tetrahedron:
Asymmetry 1997, 8, 2833.
7. (a) Igarashi, Y.; Asano, F.; Shimoyamada, M.; Harada,
M.; Nakano, S.; Iwai, R.; Yagami, K.; Konno, Y. EP
658537 1994; Chem. Abstr. 1995, 123, 313569; (b)
Senanayake, C. H.; Roberts, F. E.; DiMichele, L. M.;
Ryan, K. M.; Liu, J.; Fredenburgh, L. E.; Foster, B. S.;
Douglas, A. W.; Larsen, R. D.; Verhoeven, T. R.; Reider,
P. J. Tetrahedron Lett. 1995, 36, 3993; (c) Senanayake, C.
H.; DiMichele, L. M.; Liu, J.; Fredenburgh, L. E.; Ryan,
K. M.; Roberts, F. E.; Larsen, R. D.; Verhoeven, T. R.;
Reider, P. J. Tetrahedron Lett. 1995, 36, 7615.
8. Lakshman, M. L.; Zajc, B. Tetrahedron Lett. 1996, 37,
2529.
Lipase PS (15.1 g) was added to a solution of 5 (15.1 g,
0.1 mol) and vinyl acetate (8.6 g, 0.1 mol) in tert-butyl
methyl ether (300 ml). The mixture was stirred at 35°C
for an hour until conversion reached ca. 50%. After
filtering off the enzyme, evaporation of the solvent gave
a residue which was subjected to chromatographic
purification using hexane/ethyl acetate (2:1) to afford
(1R,2S)-(+)-5 (7.0 g, 46%, e.e.=89%), [h]D +51 (c 1.0,
CHCl3), (1S,2R)-(−)-6a (9.1 g, 47%, e.e.=91%), [h]D
−61 (c 1.0, CHCl3), and (1S,2R)-(+)-7 (0.7 g, 3%,
e.e.=100%), [h]D +69 (c 1.0, CHCl3).
3.5. Preparation of (1S,2R)-cis-1-amino-2-indanol 1
from (1S,2R)-6a: typical procedure
(1S,2R)-6a 3.8 g (20 mmol, 91% e.e.) was dissolved in
CH3CN (20 ml) and 98% sulfuric acid (3.06 g, 30
mmol) was added dropwise to the solution at 15°C.
After additional stirring at rt for 3 hours, H2O (30 ml)
was added. The mixture was stirred at 50°C for 8
hours. The reaction mixture was washed with CH2Cl2
(2×40 ml) and the aqueous layer was adjusted to pH 10
by the addition of 25% aqueous sodium hydroxide
9. Winstein, S.; Roberts, R. M. J. Am. Chem. Soc. 1953, 75,
2298.
10. (a) Suter, C. M.; Lutz, G. A. J. Am. Chem. Soc. 1938, 60,
1360; (b) Guss, C. O.; Rosenthal, R. J. Am. Chem. Soc.
1955, 77, 2549; (c) Drehahl, D.; Heublein, G.; Noll, B. J.
Prakt. Chem. 1963, 21, 208.