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J. Boyer et al.
LETTER
was extracted with Et2O (30 mL) and EtOAc (2 × 30 mL).
The combined organic layers were dried over Na2SO4. After
filtration and evaporation of the solvent, the residue was
purified by column chromatography on silica gel (hexane–
EtOAc, 75:25) to afford pure 9a (1.366 g, 3.75 mmol, 95%
yield) as colorless oil; [a]D20 –120 (c 0.5, CHCl3). 1H NMR
(400 MHz, CDCl3): d = 1.29 (s, 3 H), 1.31 (s, 3 H), 2.40 (s,
1 H), 3.26 (s, 3 H), 3.28 (s, 3 H), 3.63 (m, 1 H), 3.98 (m, 1
H), 4.35 (m, 1 H), 4.95 (d, J = 2.0 Hz, 2 H), 7.45 (m, 2 H),
7.56 (m, 1 H), 8.04 (m, 2 H). 13C NMR (100 MHz, CDCl3):
d = 17.7, 17.9, 48.3, 48.4, 52.7, 60.1, 62.5, 70.5, 80.7, 83.8,
98.2, 99.7, 128.7. 129.6, 130.0, 133.6, 165.9. IR (NaCl):
3438, 2940, 2833, 1726, 1260 cm–1. HRMS (ESI+): m/z calcd
for C19H24NaO7 [M + Na]+: 387.1408; found: 387.1414.
Prasad, K. R.; Carroll, P. J. J. Org. Chem. 2002, 67, 7802.
(e) Raghavan, S.; Joseph, S. C. Tetrahedron Lett. 2003, 44,
6173. (f) Ichikawa, Y.; Ito, T.; Isobe, M. Chem. Eur. J. 2005,
11, 1949. (g) Li, S.; Hui, X.-P.; Yang, S.-B.; Jia, Z.-J.; Xu,
P.-F.; Lu, T.-J. Tetrahedron: Asymmetry 2005, 16, 1729.
(18) (a) Harwood, L. M.; Robertson, S. M. Chem. Commun.
1998, 2641. (b) Bose, A. K.; Banik, B. K.; Mathur, C.;
Wagle, D. R.; Manhas, M. S. Tetrahedron 2000, 56, 5603.
(c) Tarrade, A.; Dauban, P.; Dodd, R. H. J. Org. Chem.
2003, 68, 9521.
(19) Lei, A. W.; Liu, G. S.; Lu, X. Y. J. Org. Chem. 2002, 67,
974.
(20) Dalcanale, E.; Montanari, F. J. Org. Chem. 1986, 51, 567.
(21) Synthesis of (2R,3R,4R)-(+)-3-Hydroxy-4-hydroxy-
methyl-2-tosylaminobutyrolactone (12).
(11) (a) An experiment performed at 60 °C using 20 mol%
Zn(OTf)2 and (–)-N-methylephedrine according with
Carreira’s catalytic protocol (see ref. 11b) showed lower
yield and stereoselectivity. (b) Anand, N. K.; Carreira, E. M.
J. Am. Chem. Soc. 2001, 123, 9687.
(12) It is noteworthy that reactions of aldehyde 2 with
nucleophilic reagents predominantly give the anti-isomer. A
delicate balance of a-coordination (pro syn) and b- or a,b-
coordination (both pro anti) is probably involved, leading to
a broad range of selectivities depending of the reagent and
experimental conditions: see ref. 5, pp. 456-458.
(13) Ley, S. V.; Woods, M.; Zanotti-Gerosa, A. Synthesis 1992,
52.
To a solution of 15 (256 mg, 0.56 mmol) in THF (12 mL), 5
mL of 6 M LiOH were added. The mixture was then heated
to reflux for 3 h. After cooling down to r.t., the mixture was
acidified with 0.2 M HCl to pH 2. This solution was then
extracted with CH2Cl2 (3 × 10 mL) and EtOAc (1 × 10 mL).
The organic layers were then dried over anhyd MgSO4,
filtrated and concentrated under reduced pressure. The crude
was dissolved in THF (40 mL) and 2 M HCl (10 mL) and the
mixture was heated for 2.5 h at 60 °C. After cooling down,
the mixture was extracted with CH2Cl2 (3 × 30 mL) and
EtOAc (1 × 20 mL). The combined organic layer was dried
over MgSO4. After filtration and evaporation of solvent, the
residue was purified by column chromatography on silica
gel (CH2Cl2–MeOH, 95:5) to afford pure lactone 12 (106
mg, 0.35 mmol, 63% yield); mp 167–168 °C; [a]D20 +26.1 (c
1.0, MeOH). 1H NMR (400 MHz, CDCl3): d = 2.32 (s, 3 H),
3.75 (m, 2 H), 4.30 (m, 2 H), 4.36 (m, 1 H), 7.25 (dd, J = 7.4,
1.8 Hz, 2 H), 7.70 (dd, J = 7.4, 1.8 Hz, 2 H). 13C NMR (100.6
MHz, CDCl3): d = 24.3, 62.9, 63.2, 79.9, 84.6, 131.0, 133.3,
142.8, 147.5, 177.4. IR (KBr): 3487, 3292, 2935, 1781,
1598, 1453, 1331, 1094, 922, 814, 664 cm–1. HRMS (FAB+):
m/z calcd for C12H16NO6S [M + 1]+: 302.0698; found:
302.0697.
(14) (a) Isono, K.; Asahi, K.; Suzuki, S. J. Am. Chem. Soc. 1969,
91, 7490. (b) Isono, K.; Suzuki, S. Heterocycles 1979, 13,
333.
(15) Mori, M.; Kakiki, K.; Misato, T. Agric. Biol. Chem. 1974,
38, 699.
(16) Shenbagamurthi, P.; Smith, H. A.; Becker, J. M.; Steinfeld,
A.; Naider, F. J. Med. Chem. 1983, 26, 1518.
(17) (a) For a review, see: Casiraghi, G.; Zanardi, F.; Rassu, G.;
Spanu, P. Chem. Rev. 1995, 95, 1677. For recent synthetic
work, see: (b) Pepper, A. G.; Procter, G.; Voyle, M. Chem.
Commun. 2002, 1066. (c) Kim, K. S.; Lee, Y. J.; Kim, J. H.;
Sung, D. K. Chem. Commun. 2002, 1116. (d) Davis, F. A.;
Synlett 2006, No. 12, 1895–1898 © Thieme Stuttgart · New York