3748
T. Olejniczak, Z. Ciunik / Tetrahedron: Asymmetry 15 (2004) 3743–3749
1.43 and 1.55 (2ddd, J = 13.9; 9.8; 4.5Hz, 1H and
J = 13.9; 9.8; 2.7Hz, 1H, –CH2CH–), 1.78–1.91 (m,
1H, (CH3)2CH–), 2.08 (s, 3H, –C(O)CH3), 2.25and
2.72 (2dd, J = 19.8; 6.7Hz, 1H and J = 19.8; 6.9Hz,
1H, –CH2C(O)–), 2.59–2.68 (m, 1H, –CH(CH3)–), 4.41
(dd J = 7.0; 5.0Hz, 1H, >CH (O–)–) 5.16 (ddd,
J = 9.5; 7.0; 2.9Hz, 1H, –CH(OAc)–); IR (film, cmÀ1):
1792 (s), 1752 (s), 1236 (s), 1024 (s).
75cm3 cultures of Fusarum solani. After a 6-day
hydrolysis of ( )-1a the products were extracted with
diethyl ether (3 · 50cm3 each flask) and dried
(MgSO4). The solvent was evaporated off and the
crude product mixture was separated by column chro-
matography. After purification there was obtained
48.2mg (20% yield) of unreacted (À)-1a isomer
24:1
D
[ee = 93%, ½a ¼ À31:1 (c 2.68, CHCl3)], 126.9mg
of d-hydroxy-c-lactone 2a with 40% of enantiomeric
excess of the (+) isomer and 30mg of not separated
products.
trans-5-(10-Acetoxy-30,30-dimethylbutyl)-4-methyl-tetra-
hydrofuran-2-one 1d: yield: 90%; n2D0 ¼ 1:4451; 1H
NMR (d, ppm): 0.92 (s, 9H, (CH3)3C–), 1.2 (d,
J = 6.8Hz, 3H, –CH(CH3)–), 1.44 and 1.62 (2dd,
J = 15 .2; 1.9Hz, 1H andJ = 15.2; 8.9Hz, 1H,
–CH2CH(OAc)–), 2.06 (s, 3H, –C(O)CH3), 2.16 and
2.73 (2dd, J = 17.5 ; 8.8Hz, 1H andJ = 17.5; 7.8Hz,
1H, –CH2C(O)–), 2.32–2.46 (m, 1H, –CH(CH3)–),
4.06 (dd, J = 6.3; 3.8Hz, 1H, –CH(O–)–) 5.17 (ddd,
J = 8.9; 3.8; 1.9Hz, 1H, –CH(OAc)–), IR (film,
cmÀ1): 1796 (s), 1752 (s), 1240 (s), 1028 (s).
Following the same procedure, there were obtained:
(S)-((10R)-Acetoxy-30-methylbutyl)-4,4-dimethyl-tetra-
hydrofuran-2-one (+)-1a: After 7-days hydrolysis with
F. tricinctum there was obtained 37.3mg, yield (15%)
21:1
D
ee = 100%, ½a
¼ þ30:6 (c 2.52, CHCl3).
trans-(5R)-((10S)-Acetoxy-30-methylbutyl)-(4R)-methyl-
tetrahydrofuran-2-one (À)-1b: After 4-days hydrolysis
23:2
cis-5-(10-Acetoxy-30,30-dimethylbutyl)-4-methyl-tetrahydro-
furan-2-one 1e: yield: 93%, n2D0 ¼ 1:4453, 1H NMR
(d, ppm): 0.93 (s, 9H, (CH3)3C–), 1.13 (d, J = 6.9Hz,
3H, –CH(CH3)–), 1.55 and 1.69 (2dd, J = 15 .0;
2.1Hz, 1H and J = 15.0; 9.3Hz, 1H, (CH3)3CCH2–),
2.05(s, 3H, –C(O)C H3), 2.22 and 2.70 (2dd, J = 16.5;
7.4Hz, 1H and J = 16.5and 5.6Hz, 1H, –C H2C(O)–),
2.67–2.72 (m, 1H, –CH(CH3)–), 4.4 (dd, J = 5.6; 5.5Hz,
1H, >CH(O–)–), 5.27 (ddd, J = 9.3; 5.5; 2.1Hz, 1H,
–CH(OAc)–); IR (film, cmÀ1): 1792 (s), 1752 (s), 1240
(s), 1048 (s).
with F. solani there was obtained 58mg yield (23%)
of (À)-1b, ee = 95 .3%,½a ¼ À26:1 (c 2.44, CHCl3).
D
cis-(5R)-((10S)-Acetoxy-30-methylbutyl)-(4S)-methyl-tetra-
hydrofuran-2-one (À)-1c: After 6-days hydrolysis with F.
24:1
solani there was obtained 43mg yield (17%) of (À)-1c
ee = 100%, ½a ¼ À34:9 (c 2.05, CHCl3).
D
trans-(5S)-((10R)-Acetoxy-30,30-dimethylbutyl)-(4S)-meth-
yl-tetrahydrofuran-2-one (+)-1d: After 4-days hydrolysis
with F. tricinctum there was obtained 27.5mg yield
22:6
(11%) of (+)-1d ee = 97.2%, ½a ¼ þ31:5 (c 3.08,
D
4.4. Enzymatic hydrolysis
CHCl3).
A typical enzymatic hydrolyse procedure of d-acetoxy-
c-lactone 1a: 10mg of enzyme was added to 3cm3 of
phosphorus buffer (7.2) solution or one of the follow-
ing organic solvents: C6H5CH3, c-C6H12, CH3CN,
(C2H5)2O, CH3CO2CH3 or THF containing 20mg of
substrate. The suspension was stirred both at room tem-
perature and at 36ꢂC. The samples were collected and
filtered over Celite. The Celite was additionally washed
with diethyl ether and the crude mixture was analysed
by GC.
Acknowledgements
This work was supported by the Polish State Committee
for Scientific Research, Grant No. 6 P06B 031 20 and
060/T09/2001/15. The authors thank Professor Jacek
´
Gawronski (A. Mickiewicz University, Poznan) for the
CD spectra measurements.
´
References
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