Z. Han et al. / Tetrahedron 61 (2005) 6386–6408
6407
heptane (150 mL) was added and the distillation was
performed under azotropic condition with a Dean–Stark
trap until all the water was removed. The resulting mixture
was then cooled to 0 8C and stirred for 1 h. The slurry was
filtered to afford (S)-TBSA (15.7 g, 76%) in 99% ee.
1
4.18.8. (S)-4-Benzyloxy-2-methyl-butanesulfinamide. H
NMR (CDCl3): d 1.23 (s, 3H), 1.24 (s, 3H), 1.93 (dt, J1Z
2.77 Hz, J2Z6.60 Hz, 2H), 1.71 (t, JZ6.59 Hz, 2H), 3.97
(s, 2H), 4.50 (m, 2H), 7.26–7.38 (m, 5H). 13C NMR
(CDCl3): d 20.2, 20.3, 34.8, 57.7, 66.3, 73.2, 127.8, 128.5,
138.5. Anal. Calcd for C12H19NO2S; C, 59.72; H, 7.93; N,
5.80; S, 13.29. Found: C, 60.12; H, 8.09; N, 5.79; S, 13.63.
References and notes
1. (a) Solladie, G. Synthesis 1981, 185. (b) Posner, G. H. In
Morrison, J. D., Ed.; Asymmetric Synthesis; Academic: New
York, 1983; Vol. 2, Chapter 3, p 225. (c) Barbachyn, M. R.;
Johnson, C. R. In Morrison, J. D., Scott, J. W., Eds.;
Asymmetric Synthesis; Academic: New York, 1983; Vol 4,
Chapter 3, p 227. (d) Carreno, M. C. Chem. Rev. 1995, 95,
1717. (e) Kagan, H. B.; Diter, P. In Page, P. C. B., Ed.;
Organosulfur Chemistry; Academic: New York, 1998; Vol. 2,
Chapter 3, p 1. (f) Khiar, N.; Fernandez, I.; Alcudia, A.;
Alcudia, F. In Rayner, C. M., Ed.; Advances in Sulfur
Chemistry; JAJ: Stamford, 2000; Vol 2. (g) Capozzi, M. A. M.;
Cardellicchio, C.; Naso, F.; Spina, G.; Tortorella, P. J. Org.
Chem. 2001, 66, 5933.
4.19. Unoptimized chromatography free process for the
preparation of (S)-TBSA
4.19.1. Preparation of (1R,2S,S)-19a. To a solution of
(2R,4S,5R)-18 (62 g, 171 mmol) in THF (350) at K45 8C
was added t-butyl magnesium chloride (200 mL, 1.0 M)
dropwise over 1–1.5 h under argon. After the reaction
mixture was stirred for 1.5 h, aqueous solution of NH4Cl
(20%) (150 mL) was added to quench the reaction (keep the
temperature below K10 8C). The reaction mixture was
diluted with THF (150 mL) and allowed to warm to ambient
temperature. After removal of the aqueous phase, the
organic phase was washed once with aqueous solution of
NaCl (24%) (75 mL) and concentrated under reduced
pressure. Then heptane was added to the mixture and the
mixture was further distilled under reduced pressure until
the mixture reached a KF value of !0.02%. Then the
concentration of the product (1R,2S,S)-19a was adjusted to
0.2 to 0.3 g/mL by adding anhydrous THF (95–98%
reaction yield).
2. (a) James, B. R.; McMillan, R. S. Can. J. Chem. 1977, 55,
3927. (b) Khiar, N.; Fernandez, I.; Alcudia, F. Tetrahedron
Lett. 1993, 34, 123. (c) Carreno, M. C.; Garcia-Ruano, J. L.;
Maestro, M. C.; Martin Cabrejas, L. M. Tetrahedron:
Asymmetry 1993, 4, 727. (d) Tokunoh, R.; Sodeoka, M.;
Aoc, K.; Shibasaki, M. Tetrahedron Lett. 1995, 36, 8035. (e)
Ordonez, M.; Rosa, V. G.; Labastida, V.; Llera, J. M.
Tetrahedron: Asymmetry 1996, 7, 2675. (f) Owens, D. T.;
Hollander, J. F.; Oliver, A. G.; Ellman, J. A. J. Am. Chem. Soc.
2001, 123, 1539.
3. (a) Savage, P. B.; Holmgren, S. K.; Gellman, S. H. J. Am.
Chem. Soc. 1993, 115, 7900. (b) Savage, P. B.; Holmgren,
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J. R.; Kurtz, L. J.; Pfister, J. R. J. Am. Chem. Soc. 1988, 110,
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Matsugi, M.; Fukuda, N.; Muguruma, Y.; Yamaguchi, T.;
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Cotton, H.; Elebring, T.; Larsson, M.; Li, L.; Sorensen, H.;
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4.19.2. Preparation of (S)-TBSA. To an ammonia
(600 mL) solution at K45 8C containing catalytic amount
of Fe(NO3)3 was added lithium (5.25 g) portionwise under
argon and the resulting mixture was stirred at K45 8C for
1.5 h. The mixture was then cooled to K78 8C and a
solution of (1R,2S,S)-19a prepared above was added in
1.5 h. After stirring for 20 min, the reaction mixture was
warmed to K45 8C and stirred for 30–60 min to furnish the
reaction. After the quenching of the reaction by slow
addition of solid ammonium chloride (60 g) portionwise,
the mixture was warmed to 20–25 8C while the released
ammonia gas was trapped by water. The mixture was diluted
with isopropyl acetate (IPAC) (500 mL) and the resulting
mixture was distilled under reduced pressure to remove the
low boiling point solvent (THF). Water (140 mL) and IPAC
(300 mL) was added to the residue and stirred to give a clear
phase separation. The organic phase was washed once with
aqueous solution of NH4Cl (24%) (30 mL). The aqueous
phase was extracted with IPAC (150 mL!2) and the
organic phases were combined ((S)-TBSA is very soluble in
water). The combined organic phases were conducted
solvent switch under pressure to water (80 mL) and stirred
to give a slurry. The slurry was filtered and wet cake was
washed twice with water (15 mL). The wet cake was dried
and recovered as the starting material (1R,2S)-17 (50.5 g
97%), leaving the (S)-TBSA in the aqueous solution. The
aqueous solution of (S)-TBSA was vacuum concentrated,
5. Kagan, H. B. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.
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Synthesis; AP: UK, 1994. (b) Kagan, H. B.; Rebiere, F. Synlett
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1926, 48, 2715.
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