5808
K. Yamato et al. / Tetrahedron Letters 43 (2002) 5805–5808
give 11s quantitatively that was used without further
5. (a) Dietz, M. L.; Bond, A. H.; Hay, B. P.; Chiarizia, R.;
Huber, V. J.; Herlinger, A. W. Chem. Commun. 1999,
1177–1178; (b) Bond, A. H.; Chiarizia, R.; Huber, V. J.;
Dietz, M. L.; Herlinger, A. W.; Hay, B. P. Anal. Chem.
1999, 71, 2757–2765.
purification.
14. A solution of 11s (700 mg, 2.5 mmol) in DMSO (10 mL)
was added to a suspension of 60% NaH (0.30 g, 7.5 mmol)
in DMSO (100 mL). After 0.5 h, 9 (1.03 g, 2.5 mmol) was
added and the reaction mixture was stirred for 40 h at room
temperature. Brine was added and the mixture was
extracted three times with Et2O. The combined extracts
were washed with brine, dried over MgSO4 and evaporated
in vacuo. The residue was purified by column chromatog-
raphy (Al2O3, hexane:ethyl acetate (10:14:1)). Yield 38%,
mp 68–70°C (lit.6 mp 71–74°C). [h]2D5=+43.0 (c=0.230,
EtOH) (lit.6 [h]D20=+39.2 (c=1, EtOH)).
6. Hayward, R. C.; Overton, C. H.; Whitham, G. H. J. Chem.
Soc., Perkin Trans. 1 1976, 2413–2415.
7. Huber, V. J.; Dietz, M. L. Tetrahedron Lett. 2001, 42,
2945–2948.
8. Yamato, K.; Bartsch, R. A.; Dietz, M. L.; Rogers, R. D.
Tetrahedron Lett. 2002, 43, 2153–2156.
9. Posner, G. H.; Rogers, D. Z. J. Am. Chem. Soc. 1977, 99,
8208–8214.
15. A colorless single crystal (0.25×0.11×0.03 mm) was
obtained by recrystallization from heptane. Diffraction
data were collected with a Siemens CCD area detector-
10. Optical resolution of 7 was accomplished by adapting a
literature procedure.11 Racemic 7 (1.24 g, 6.0 mmol) and
vinyl acetate (1.53 g, 18 mmol) were dissolved in 8 mL of
tert-butyl methyl ether. The solution was circulated
through a glass column filled with lipase (Amano Lipase
PS-D1 (immobilized on diatomite) purchased from
Aldrich, 1 g) with a peristaltic pump for 24 h. The solution
was evaporated in vacuo and the residue was purified by
column chromatography (SiO2:hexane–ethyl acetate
(20:14:1)) to yield 7s (35%) and 8r (35%). 8r was
dissolved in 10 mL of methanol and K2CO3 was added. The
mixture was stirred overnight and filtered The filtrate was
evaporated in vacuo to give 7r quantitatively.
,
equipped diffractometer with MoKa (u=0.071073 A)
radiation at −100°C using a stream of nitrogen gas. The
crystal structure was solved by direct methods using the
SHELXTL software package. All non-hydrogen atoms
were anisotropically refined and hydrogen atoms were
,
calculated (dCꢀH=0.97 A) and fixed with the thermal
parameters based upon the carbon atom to which they are
bonded. Crystal data for 4s: formula C20H36O6, Fw=
372.49, orthorhombic, space group P212121 (c19), a=
3
,
,
9.333(6), b=10.160(7), c=21.955 (14) A, V=2082(2) A ,
Z=4, Dcalcd=1.188 g cm−3, R1=0.0736, wR2=0.1989
(I>2|(I)). One ethylene group was observed to be disor-
dered and refined in two alternate orientations with 50%
occupancy each. Though it appears that O(2) may also be
fractionally disordered, this disorder could not be resolved.
Crystallographic data (excluding structure factors) for the
structures in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplemen-
tary publication number CCDC 184304. A copy of the data
can be obtained, free of charge, from CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [fax: +44 (0) 1223-336033
or e-mail: deposit@ccdc.cam.ac.uk].
11. Laumen, K.; Seemayer, R.; Schneider, M. P. J. Chem. Soc.,
Chem. Commun. 1990, 49–51.
12. Compound 10s was synthesized by a literature method.7 A
solution of 7s (2.40 g, 11.6 mmol) in DMSO (15 mL) was
added to a suspension of 60% NaH (1.00 g, 25 mmol) in
DMSO (100 mL). After 0.5 h, 9 (2.41 g, 5.8 mmol) was
added and the reaction mixture was stirred at room
temperature. After stirring overnight, a second portion of
9 (1.20 g, 2.9 mmol) was added. The mixture was stirred
for 10 h at room temperature. Water was added and the
mixture was extracted three times with Et2O. The com-
bined extracts were washed with brine, dried over MgSO4
and evaporated in vacuo. The residue was purified by
column chromatography (Al2O3, hexane:ethyl acetate
(45:120:1)). Yield 40%.
16. Ortep 3 for Windows: Farrugia, J. L. J. Appl. Cryst. 1997,
30, 565.
17. Dunitz, J. D.; Seiler, P. Acta Crystallogr., Sect. B 1974, 30,
2739–2741. CCDC reference code: HOXOCD.
18. (a) Coxon, A. C.; Laidler, D. A.; Pettman, R. B.; Stoddart,
J. F. J. Am. Chem. Soc. 1978, 100, 8260–8262; (b) Dale,
J. Isr. J. Chem. 1980, 20, 3–11.
13. To a methanol solution of 10s, 10% Pd–C and a few drops
of acetic acid were added. The mixture was shaken for 12
h under H2 (70 psi). The catalyst was removed by filtration
through Celite and the filtrate was evaporated in vacuo to
Yamato, Kazuhiro
