1374
K. Kadota et al.
SHORT PAPER
under reduced pressure, the residue was chromatographed (SiO2,
15 g, elution with Et2O/hexane, 1:3 v/v) to give the acetate (±)-7
(500 mg, 94%) as a pale yellow oil.
tane, 1:5 v/v) to give (-)-(1S,5S)-2 (206 mg, 84%), [a]D30 -428.0 (c
= 1.10, CHCl3) [Lit.5 [a]D28 -312.0 (c = 1.0, CHCl3), 93% ee], as a
colorless oil.
IR (film): n = 1738 cm-1.
(+)-(1R,5R)-Isolevoglucosenone from (-)-(1R,4R,5R)-6
To a stirred solution of (-)-(1R,4R,5R)-6 (330 mg, 2.58 mmol) in
CH2Cl2 (15 mL) was added MnO2 (4.48 g, 51.6 mmol) at r.t. and the
mixture was stirred at the same temperature. On treatment as above
for (-)-(1S,5S)-2, (+)-(1R,5R)-2 (266 mg, 82%), [a]D31 +425.0 (c =
1.10, CHCl3) [Lit.5 [a]D31 +321.0 (c = 1.1, CHCl3), 90% ee], was ob-
tained as a colorless oil.
1H NMR (300 MHz, CDCl3): d = 5.98 (1 H, ddd, J = 9.6, 3.0, 1.6
Hz), 5.77-5.75 (1 H, m), 5.69 (1 H, dt, J = 9.6, 1.9 Hz), 5.55 (1 H,
d, J = 3.0 Hz), 4.69-4.65 (1 H, m), 4.16 (1 H, dd, J = 8.0, 1.9 Hz),
3.96-3.91 (1 H, m), 2.10 (3 H, s).
HRMS: m/z calcd for C8H10O4: 170.0578, found: 170.0571.
Anal. calcd for C8H10O4: C 56.47 H 5.92, found: C 56.51 H 5.86.
Kinetic Transesterification of the Racemic Alcohol (±)-6
Acknowledgement
A solution of (±)-6 (700 mg, 5.46 mmol) and vinyl acetate
(5.03 mL, 54.6 mmol) in THF (11 mL) was stirred with Lipase AK
(immobilized on Celite, Pseudomonas sp., Amano) (350 mg) at r.t.
for 33 h. After filtration through a Celite-pad, the filtrate was
evaporated under reduced pressure and chromatographed (SiO2,
30 g, elution with Et2O/hexane, 1:3-1:1 v/v) to give the acetate
We are grateful for the Egyptian Associate Channel System Pro-
gram Scholarship (to A. S. ElAzab).
References
30
(-)-(1R,4R,5R)-7 (445 mg, 48%), [a]D -49.0 (c = 1.12, CHCl3),
(1) Shafizadeh, F.; Chin, P. P. P. Carbohydr. Res. 1977, 58, 79.
(2) Pertinent reviews, see:
as a pale yellow oil and the alcohol (+)-(1S,4S,5S)-6 (328 mg, 47%),
[a]D32 +18.1 (c = 1.08, CHCl3), as a colorless solid. Optical purity of
the products was determined by HPLC using a column with chiral
stationary phase [CHIRALCEL OD, elution with i-PrOH/hexane
(3:97, v/v) (0.5 mL/min), retention time 18.8 min for (+)-6 and 22.8
min for (–)-6)] both having >99% ee after transformation into the
benzoate.
(a) Witczak, Z. J. In Studies in Natural Products Chemistry;
Atta-ur-Rahman, Ed.; Elsevier: Amsterdam, 1994, Vol. 14, pp
268-282.
(b) Witczak, Z. J. Pure & Appl. Chem. 1994, 66, 2189.
(c) Ebata, T.; Matsushita, H. J. Syn. Org. Chem. Jpn. 1994, 52,
1074.
(3) Shibagaki, M.; Takahashi, K.; Kuno, H.; Honda, I.;
Matsushita, H. Chem. Lett. 1990, 307.
(4) A route to (+)-enantiomer, see: Witczak, Z. J. Synlett 1996,
108.
(5) Taniguchi, T.; Nakamura, K.; Ogasawara, K. Synlett 1996,
971.
(6) (a) Ranganayokulu, K.; Singh, U. P.; Murray, T. P.; Brown, R.
K. Can. J. Chem. 1974, 52, 988.
Kinetic Hydrolysis of the Racemic Acetate (±)-7
A mixture of (±)-7 (880 mg, 5.17 mmol) and Lipase AK (immobi-
lized on Celite, Pseudomonas sp., Amano) (880 mg) in 0.1 M phos-
phate buffer solution (pH 7.2, 18 mL) and acetone (2 mL) was
stirred at r.t. for 24 h. After filtration though a Celite-pad, the filtrate
was evaporated and chromatographed (SiO2, 40 g, elution with
Et2O/hexane, 1:3-1:1 v/v) to give the alcohol (-)-(1R,4R,5R)-6
(339 mg, 51%), [a]D31 -18.4 (c = 1.00, CHCl3), as a colorless solid
and the acetate (+)-(1S,4S,5S)-7 (425 mg, 48%), [a]D29 +50.0 (c =
1.20, CHCl3), as a pale yellow oil. Optical purity of the products
was determined by HPLC using a column with chiral stationary
phase (CHIRALCEL OD, elution with i-PrOH/hexane (3:97, v/v)
(-)-(1R,4R,5R)-6 as 97% ee and (+)-(1S,4S,5S)-7 as 98% ee, re-
spectively.
(b) Köll, P.; Schultek, T.; Rennecke, R. -W. Chem. Ber. 1976,
337.
(c) Horton, D.; Roski, J. P.; Norris, P. J. Org. Chem. 1996, 61,
3783.
(7) For a pertinent review, see: Kolb, H. C.; VanNieuwenhze, M.
S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483.
(8) Ohloff, G.; Uhde, G. Helv. Chim. Acta 1970, 53, 531.
Kawamura, M.; Ogasawara, K. J. Chem. Soc., Chem.
Commun. 1995, 2403.
(9) Practically, only (+)-isolevoglucosenone is obtained from D-
glucose. See Ref. 6.
(10) For pertinent monographs, see: Wong, C. H.; Whitesides, G.
Enzymes in Synthetic Organic Chemistry; Pergamon: Oxford,
1994.
Conversion of (-)-(1R,4R,5R)-7 into (-)-(1R,4R,5R)-6
A solution of (-)-(1R,4R,5R)-7 (360 mg, 2.12 mmol) in MeOH
(12 mL) was stirred with K2CO3 (1.47 g, 10.6 mmol) at r.t. for
10 min. The mixture was diluted with H2O (2 mL) and extracted
with Et2O (2 î 30 mL). The extract was washed with brine (2 î
10 mL), dried (MgSO4), evaporated under reduced pressure, and
chromatographed (SiO2, 10 g, elution with Et2O/hexane, 1:2 v/v) to
give (-)-(1R,4R,5R)-6 (250 mg, 92%) as a colorless solid.
Patel, R. N. Stereoselective Biocalaysis; Marcel Dekker: New
York, 1999.
(11) Taniguchi, T.; Takeuchi, M.; Kadota, K.; ElAzab, A. S.;
Ogasawara, K. Synthesis 1999, 1325.
(12) Schmidt, U.; Werner, J. Synthesis 1986, 986.
See also: Harris, S. M.; Keranen, M. D.; O’Doherty, G. A. J.
Org. Chem. 1999, 64, 2982.
Conversion of (+)-(1S,4S,5S)-7 into (+)-(1S,4S,5S)-6
A solution of (+)-(1S,4S,5S)-7 (420 mg, 2.47 mmol) in MeOH
(15 mL) was stirred with K2CO3 (1.71 g, 12.4 mmol) at r.t.
for 10 min. On treatment as above for (-)-(1R,4R,5R)-6,
(+)-(1S,4S,5S)-6 (291 mg, 92%) was obtained as a colorless solid.
(13) Luche, J. -L. J. Am. Chem. Soc. 1977, 100, 2226.
Gemal, A. L.; Luche, J. -L. J. Am. Chem. Soc. 1981, 103,
5454.
(-)-(1S,5S)-Isolevoglucosenone from (+)-(1S,4S,5S)-6
To a stirred solution of (+)-(1S,4S,5S)-6 (250 mg, 1.95 mmol) in
CH2Cl2 (15 mL) was added MnO2 (3.39 g, 39.0 mmol) at r.t. and the
mixture was stirred at the same temperature for 2 h. After filtration
through a Celite-pad, the filtrate was evaporated under reduced
pressure and chromatographed (SiO2, 10 g, elution with Et2O/pen-
Article Identifier:
1437-210X,E;2000,0,10,1372,1374,ftx,en;F01800SS.pdf
Synthesis 2000, No. 10, 1372–1374 ISSN 0039-7881 © Thieme Stuttgart · New York