G. Fonseca, G. A. Seoane / Tetrahedron: Asymmetry 16 (2005) 1393–1402
1401
1H), 4.82 (d, J = 4 Hz, 1H); 13C NMR (CDCl3) d ꢀ5.1
(CH3), ꢀ4.2 (CH3), 18.8 (C), 26.1 (3 · CH3), 27.2
(CH2), 27.8 (CH2), 55.9 (CH3), 65.2 (CH), 79.1 (CH),
79.4 (CH), 97.0 (CH2), 202.1 (C). Due to the instability
of the azido group, it was not possible to obtain an ana-
lytically pure sample suitable for combustion analysis.
Prof. T. Hudlicky for providing the cultures of P. putida
F39/D.
References
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Chiron Approach; Pergamon: New York, 1983, Chapter 2;
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Koike, T.; Murata, K.; Ikariya, T. Org. Lett. 2000, 2,
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Love, B. E. J. Chem. Soc., Chem. Commun. 1987, 1288; (c)
Steglich, W.; Hofle, G. Angew. Chem., Int. Ed. Engl. 1969,
8, 981.
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Kitano, K.; Nakamura, K.; Ohno, A. Bull. Chem. Soc.
Jpn. 1999, 72, 99; (b) Zhu, Y.; Tu, Y.; Yu, H.; Shi, Y.
Tetrahedron Lett. 1998, 39, 7819; (c) Adam, W.; Fell, R.
T.; Saha-Moller, C. R.; Zhao, C.-G. Tetrahedron: Asym-
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4.17. (1S,2S,3S,4R)-1,2-O-Isopropylidenecyclohexane-
1,2,3,4-tetraol, 9 and (1S,2S,3R,4R)-1,2-O-isopropylid-
enecyclohexane-1,2,3,4-tetraol, 10
To a solution of ketone 4 (0.4 g, 2.2 mmol) in MeOH
(30 mL) was added NaBH4 (90 mg, 2.4 mmol) in por-
tions at rt. After 15 min of stirring, the mixture was con-
centrated under reduced pressure and the residue was
taken in Et2O (50 mL). The organic layer was succes-
sively washed with 10% NaHCO3 (2 · 25 mL) and brine
(2 · 10 mL), dried, and concentrated under reduced
pressure. The residue was purified by column chroma-
tography (SiO2; EtOAc) to afford 9 and 10 as white sol-
1
ids. Compound 9 (0.26 g, 40%), Rf = 0.2 (EtOAc); H
NMR (CDCl3) d 1.37 (s, 3H), 1.54 (s, 3H), 1.72 (m,
2H), 1.80 (m, 1H), 2.16 (m, 1H), 3.28 (s, OH, 2H),
3.42 (m, 1H), 3.52 (m, 1H), 3.90 (m, 1H), 4.26 (m,
1H); 13C NMR (CDCl3) d 24.1 (CH2), 26.6 (CH3),
26.9 (CH2), 28.7 (CH3), 71.8 (CH), 74.4 (CH), 78.7
(CH), 81.2 (CH), 109.5 (C); Compound 10 (0.29 g,
1
45%), Rf = 0.3 (EtOAc); H NMR (CDCl3) d 1.36 (s,
3H), 1.57 (s, 3H), 1.67 (m, 2H), 1.81 (m, 1H), 1.90 (m,
1H), 2.75 (s, OH, 1H), 3.05 (s, OH, 1H), 3.75 (m, 1H),
3.88 (m, 1H), 4.24 (m, 1H), 4.33 (m, 1H); 13C NMR
(CDCl3) d 23.0 (CH2), 25.7 (CH3), 26.1 (CH2), 28.0
(CH3), 69.1 (CH), 69.3 (CH), 73.7 (CH), 77.0 (CH),
109.4 (C).
4.18. (1R,2R,3S,4R)-1,2-O-Isopropylidenecyclohexane-
1,2,3,4-tetraol, 12
To
a
solution of vinylic bromide 1713 (95 mg,
0.26 mmol) in MeOH (50 mL) was added Raney-Ni
(under aqueous NaOH, 100 mg). Hydrogen was bub-
bled through the mixture for 1 min to evacuate the air
and then the mixture was stirred in a hydrogen atmo-
sphere. After 30 min, the catalyst was filtered off and
the solution was concentrated under reduced pressure.
The residue was taken in EtOAc (40 mL), washed with
brine (2 · 20 mL), dried, and concentrated under re-
duced pressure to give a crude which was purified by
chromatography (SiO2; EtOAc) to furnish 12 as a white
solid (40 mg, 50%). Rf = 0.2 (EtOAc); 1H NMR (CDCl3)
d 1.28 (m, 1H), 1.34 (s, 3H), 1.49 (s, 3H), 1.62 (m, 1H),
1.83 (m, 1H), 1.96 (m, 1H), 3.20 (s, OH, 2H), 3.54 (m,
1H), 3.82 (m, 1H), 4.21 (m, 1H), 4.42 (m, 1H); 13C
NMR (CDCl3) d 26.1 (CH2), 26.5 (CH3), 27.5 (CH2),
28.0 (CH3), 70.2 (CH), 74.6 (CH), 75.1 (CH), 78.1
(CH), 109.7 (C).
6. (a) Adam, W.; Diaz, M. T.; Fell, R. T.; Saha-Moller, C. R.
Tetrahedron: Asymmetry 1996, 7, 2207; (b) Tanyeli, C.;
Turkut, E.; Akhmedov, I. M. Tetrahedron: Asymmetry
2004, 15, 1729.
7. (a) Schapiro, V.; Cavalli, G.; Seoane, G. A.; Faccio, R.;
Mombru, A. W. Tetrahedron: Asymmetry 2002, 13, 2453;
(b) Brovetto, M.; Schapiro, V.; Cavalli, G.; Padilla, P.;
Sierra, A.; Seoane, G. A.; Suescun, L.; Mariezcurrena, R.
New J. Chem. 1999, 23, 549.
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1968, 7, 2653; (b) Gibson, D. T.; Hensley, M.; Yhosiota,
H.; Mabry, T. J. Biochemistry 1970, 9, 1626; (c) Gibson,
D. T.; Kobak, V. M.; Davis, R. E.; Garza, A. J. Am.
Chem. Soc. 1973, 95, 4120.
9. Hudlicky, T.; Gonzalez, D.; Gibson, D. T. Aldrichim. Acta
1999, 32, 35, and references cited therein.
10. Whereas no reports have been found on the use of this
strategy to prepare the nucleous. The synthesis of a
representative side chain of bengamides has recently been
disclosed starting from bromobenzene: Banwell, M. G.;
Mc Rae, K. J. J. Org. Chem. 2001, 66, 6768.
Acknowledgements
11. Hamersma, J. W.; Snyder, E. I. J. Org. Chem. 1965, 30,
3985.
Support of this work from the Universidad de la Repu´b-
lica-CSIC (Uruguay) and PEDECIBA (Project URU/
97/016) is gratefully acknowledged. The authors thank
12. Hudlicky, T.; Mandel, M.; Rouden, J.; Lee, R. S.;
Bachmann, B.; Dudding, T.; Yost, K. J.; Merola, J. S.
J. Chem. Soc., Perkin Trans. 1 1994, 1553.