2402
T. TASHIRO et al.
92 ꢁC (88 ꢁC main) at 55 Torr; nD ¼ 1:4299. IR ꢀmax
22
J. Org. Chem., 49, 882–884 (1984).
(film) cmꢂ1: 1714 (s, C=O), 1651 (m, C=C), 1115 (m),
2) Liebich, H. M., Zlatkis, A., Bertsch, W., Van Dahm, R.,
and Whitten, W. K., Identification of dihydrothiazoles in
urine of male mice. Biomed. Mass Spectrom., 4, 69–72
(1977).
3) Novotny, M., Harvey, S., Jemiolo, B., and Alberts, J.,
Synthetic pheromones that promote inter-male aggres-
sion in mice. Proc. Natl. Acad. Sci. USA, 82, 2059–2061
(1985).
1
889 (m). H-NMR ꢁH (400 MHz, CDCl3): 1.06 (3H, t,
J ¼ 7:2 Hz, CH2CH3), 1.73 (3H, s, C=CCH3), 2.05 (2H,
t, J ¼ 7:2 Hz, 5-H2), 2.45 (2H, q, J ¼ 7:2 Hz, 2-H2),
2.56 (2H, t, J ¼ 7:2 Hz, 4-H2), 4.66 (1H, s, C=CH),
4.73 (1H, s, C=CH). HRMS: calcd. for C8H14O (Mþ),
126.1045; found, 126.1056.
4) Novotny, M. V., Xie, T.-M., Harvey, S., Wiesler, D. P.,
Jemiolo, B., and Carmack, M., Stereoselectivity in
mammalian chemical communication: male mouse pher-
omones. Experientia, 51, 738–743 (1995).
5) Wood, D. L., Browne, L. E., Ewing, B., Lindahl, K.,
Bedard, W. D., Tilden, P. E., Mori, K., Pitman, G. B.,
and Hughes, P. R., Western pine beetle: specificity
among enantiomers of male and female components
of an attractant pheromone. Science, 192, 896–898
(1976).
6) Bacchini, A., Gaetani, E., and Cavaggioni, A., Pher-
omone binding proteins of the mouse, Mus muscules.
Experientia, 48, 419–421 (1992).
7) Cavaggioni, A., Mucignat-Caretta, C., and Zagotto, G.,
Absolute configuration of 2-sec-butyl-4,5-dihydrothia-
zole in male mouse urine. Chem. Senses, 28, 791–797
(2003).
8) Novotny, M. V., Jemilio, B., Wiesler, D., Ma, W.,
Harvey, S., Xu, F., Xie, T.-M., and Carmack, M.,
A unique urinary constituent, 6-hydroxy-6-methyl-3-
heptanone, is a pheromone that accelerates puberty in
female mouse. Chem. Biol., 6, 377–383 (1999).
9) Osada, K., Tashiro, T., Mori, K., and Izumi, H., The
identification of attractive volatiles in aged male mouse
urine. Chem. Senses, in press.
10) Mori, K., and Seu, Y.-B., Pheromone synthesis, Part 96.
Synthesis of both the enantiomers of 7-ethyl-5-methyl-
6,8-dioxabicyclo[3.2.1]oct-3-ene, the Mus musculus
(house mouse) pheromone. Tetrahedron, 42, 5901–
5904 (1986).
11) Tashiro, T., and Mori, K., Pheromone synthesis,
CXCVII. Synthesis of the enantiomers of 2-sec-butyl-
4,5-dihydrothiazole and (1R,5S,7R)-3,4-dehydro-exo-
brevicomin, pheromone components of the male mouse
Mus musculus. Eur. J. Org. Chem., 2167–2173 (1999).
12) Busacca, C. A., Dong, Y., and Spinelli, E. M., A one-
step synthesis of thiazolines from esters. Tetrahedron
Lett., 37, 2935–2938 (1996).
6-Hydroxy-6-methyl-3-heptanone (4) by hydration of
18. A solution of 18 (800 mg, 6.3 mmol) in THF (4 ml)
was added to a stirred and yellowish suspension of
Hg(OAc)2 (1.7 g, 13.5 mmol) in THF (5 ml) and water
(5 ml) at 0–5 ꢁC with ice-cooling. The mixture became a
clear solution which was stirred for 30 min at room
temperature. A solution of NaBH4 (250 mg, 6.6 mmol)
and NaOH (360 mg, 9 mmol) in H2O (3 ml) was added
dropwise to the stirred and ice-cooled mixture. The
solution turned gray in color and Hg was precipitated.
The mixture was then saturated with NaCl and extracted
with diethyl ether. The extract was washed with brine,
dried (MgSO4), and concentrated in vacuo. The residue
(about 900 mg) was chromatographed over SiO2 (5.0 g).
Elution with hexane/EtOAc (50:1) gave 350 mg (44%)
of recovered starting ketone 18. Further elution with
hexane/EtOAc (50:1–10:1) gave 140 mg (15%, 23%
based on consumed 18) of desired hydroxy ketone 4.
Finally, elution with hexane/EtOAc (1:1) afforded
260 mg (28%, 42% based on consumed 18) of diol 16.
Hydroxy ketone 4 obtained by this reaction was very
pure and showed the following spectral data: IR ꢀmax
(film) cmꢂ1: 3421 (s, OH), 1711 (s, C=O), 1460 (m),
1377 (m), 1273 (w), 1136 (m), 1036 (w), 968 (m), 933
(m), 879 (w); 1H-NMR ꢁH (400 MHz, CDCl3): 0.97
(0.9H, t, J ¼ 7:6 Hz, CH2CH3 of 40), 1.07 (2.1H, t,
J ¼ 7:2 Hz, CH2CH3 of 4), 1.18 (0.9H, s, CH3 of 40)
1.22 [4.2H, HOC(CH3)2 of 4], 1.39 (0.9H, s, CH3 of 40),
1.62–1.80 (ca. 4H, m), 1.90–1.98 (0.5H, m), 2.00–2.10
(0.5H, m), 2.47 (1.4H, q, J ¼ 7:2 Hz, 2-H2 of 4), 2.50
(1.4H, t, J ¼ 7:2 Hz, 5-H2 of 4); 13C-NMR ꢁC (100
MHz, CDCl3): 7.91, 7.93, 11.0, 28.4, 29.3, 30.3, 33.9,
35.3, 36.0, 36.7, 37.3, 70.0, 82.2, 107.4, 212.2.
Acknowledgments
13) Stevens, C. M., and Tarbell, D. S., The kinetics of
basic hydrolysis of some ꢂ-lactones and ꢂ-thiolactones
in aqueous acetone. J. Org. Chem., 19, 1996–2003
(1954).
14) Basha, A., Lipton, M., and Weinreb, S. M., A mild,
general method for conversion of esters to amides.
Tetrahedron Lett., 4171–4174 (1977).
K. M. thanks Mr. M. Kimura (President, Toyo Gosei
Co.) for his support. K. M. also thanks Mr. Y. Shikichi
(Toyo Gosei Co.) for the spectral analysis. Mr. H.
Tawaragi (RIKEN) kindly measured the HRMS data.
15) Garigipati, R. S., Tschaen, D. M., and Weinreb, S. M.,
Total synthesis of (þ)-actinobolin. J. Am. Chem. Soc.,
107, 7790–7792 (1985).
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