2108
B. Ortiz et al.
PAPER
MS (EI): m/z (%) = 205 (1, M+ + 1), 145 (32), 113 (100), 85 (52),
74 (18), 43 (59).
Acknowledgment
We thank M. I. Chávez, E. García-Ríos, E. Huerta, R. Patiño, M. A.
Peña, F. J. Pérez, B. Quiroz, H. Ríos, L. Velasco, and M. N. Zavala
for their technical assistance. We also thank, Dr. J. M. Muchowski
for reviewing the manuscript.
HRMS (FAB+): m/z calcd for C9H17O5 [M + 1]: 205.1076; found:
205.1079.
(2S)-2-Methylhexane-1,2,6-triol (8)
A solution of 7 (0.612 g, 3 mmol) in THF (5 mL) was added to a
suspension of LiAlH4 (0.115 g) in THF (25 mL). The mixture was
stirred at r.t. for 24 h and quenched with aq sat. Na2SO4 (0.5 mL).
The resulting mixture was stirred at r.t. for 3 h, filtered through
Celite and washed with EtOAc (30 mL). The combined filtrates and
washings were concentrated. The crude colorless liquid (0.45 g)
was used in the next step without further purification.
1H NMR (300 MHz, CDCl3–DMSO-d6): d = 1.13 (s, 3 H), 1.35–
1.68 (m, 6 H), 3.17 (br s, 2 H), 3.36 and 3.43 (AB system, J = 10.8
Hz, 2 H), 3.77 (t, J = 6.0 Hz, 2 H).
References
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(S)-4-(2,2,4-Trimethyl-1,3-dioxolan-4-yl)butan-1-ol (9)
To a solution of 8 (0.44 g, 2.97 mmol) in acetone (10 mL) were add-
ed 2,2-dimethoxypropane (1 mL) and TsOH·H2O (0.002 g). The
mixture was stirred at r.t. for 1 h. After evaporation of the solvent,
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with Et2O (3 × 10 mL). The organic extracts were washed with brine
(10 mL), dried, and concentrated. The residue was purified by flash
chromatography using EtOAc–hexane (3:7) as eluent to give 0.421
g (75%, two steps) of 9 as a colorless oil; [a]D –3.15 (c = 2.0,
CHCl3) {Lit.8 [a]D –2.57 (c = 1.11, CHCl3); Lit.4d [a]D –2.43
(c = 1.07, CHCl3)}.
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(b) Prasad, K. R.; Chandrakumar, A.; Anbarasan, P.
Tetrahedron: Asymmetry 2006, 17, 1979. (c) Tyvorskii, V.
I.; Astashko, D. A.; Kulinkovich, O. G. Tetrahedron 2004,
60, 1473. (d) Jew, S.-s.; Lim, D.-Y.; Kim, J.-Y.; Kim, S.-j.;
Roh, E.-y.; Yi, H.-J.; Ku, J.-M.; Park, B.-s.; Jeong, B.-s.;
Park, H.-g. Tetrahedron: Asymmetry 2002, 13, 155.
(e) Ambrosi, P.; Arnone, A.; Bravo, P.; Bruche, L.; De
Cristofaro, A.; Francardi, V.; Frigerio, M.; Gatti, E.;
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T.; Ogasawara, K. Tetrahedron Lett. 2000, 41, 3631.
(h) Majewski, M.; Nowak, P. Tetrahedron: Asymmetry
1998, 9, 2611. (i) Kouklovsky, C.; Dirat, O.; Berranger, T.;
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(5) (a) García Ruano, J. L.; Martín Castro, A. M.; Rodríguez, J.
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IR (film): 3421, 2983, 2939, 2868, 1459, 1375, 1118, 1059 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.25 (s, 3 H), 1.36 (s, 3 H), 1.37
(s, 3 H), 1.40–1.62 (m, 6 H), 1.97 (br s, 1 H), 3.63 (t, J = 6.6 Hz, 2
H), 3.68 and 3.76 (AB system, J = 8.1 Hz, 2 H).
13C NMR (75 MHz, CDCl3): d = 20.7, 24.7, 27.0, 27.2, 33.0, 39.7,
62.6, 73.9, 81.2, 109.0.
MS (EI): m/z (%) = 189 (1, M+ + 1), 173 (61), 115 (100), 113 (70),
95 (89), 72 (80), 57 (38), 43 (81).
X-ray Crystal Data for 4 and 5
Data for 4 and 5 were collected at r.t. with a Bruker APEX CCD dif-
fractometer with graphite-monochromated Mo-Ka (l = 0.71073 Å)
radiation. The structures were solved by direct methods using
SHELXS-979 and refined with all data on F2 using SHELXL-97.10
All nonhydrogen atoms were treated anisotropically. The hydrogen
atoms attached to heteroatoms were located on difference Fourier
maps at advanced stages and their positional parameters refined,
while those attached to carbon atoms were geometrically idealized
and refined using a riding model.
4:11 Monoclinic, space group: P21, cell parameters: a = 11.457(1),
b = 5.4040(5), c = 12.875(1) Å, b = 93.193(2)°, V = 795.9(1) Å3,
Z = 2,
r
calcd = 1.299 gcm–3, F(000) = 332, m = 0.218 mm–1,
l = 0.71073 Å. Total number of least-squares parameters 201.
R1 = 0.0574 for 2699 Fo > 4s(Fo) and 0.1202 for all 5531 data.
wR2 = 0.0960,
GOF = 1.005
for
all
data,
Flack
parameter = 0.01(8).
5:11 Monoclinic, space group: P21, cell parameters: a = 5.498(1),
b = 14.948(1), c = 9.128(1) Å, b = 96.219(2)°, V = 745.8(2) Å3,
Z = 2,
r
calcd = 1.329 gcm–3, F(000) = 316, m = 0.232 mm–1,
l = 0.71073 Å. Total number of least-squares parameters 194.
(7) (a) Carreño, M. C.; Des Mazeri, R.; Urbano, A.; Colobert,
F.; Solladié, G. J. Org. Chem. 2003, 68, 7779. (b) Solladié,
G.; Maestro, M. C.; Rubio, A.; Pedregal, C.; Carreño, M. C.;
García Ruano, J. L. J. Org. Chem. 1991, 56, 2317.
(8) Nishimura, Y.; Mori, K. Eur. J. Org. Chem. 1998, 233.
(9) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
R1 = 0.0421 for 2325 Fo > 4s(Fo) and 0.0499 for all 2716 data.
wR2 = 0.0935,
GOF = 1.013
for
all
data,
Flack
parameter = 0.01(8).
Synthesis 2008, No. 13, 2105–2109 © Thieme Stuttgart · New York