J. Roos, F. Effenberger / Tetrahedron: Asymmetry 10 (1999) 2817–2828
2827
5.8. Enzyme catalyzed preparation of trihydroxynitrile 12 from protected (R)- and (S)-glyceraldehyde
11
(a) (R)- and (S)-11 was reacted with HCN in diisopropyl ether under (R)-PaHNL and (S)-MeHNL
catalysis as described in the literature23 to yield the respective diastereomers 12.
20
1
(2S,3R)-12: [α] =−15.5 (c 1.15, CHCl3), 60% de; H NMR (CDCl3): δ=1.39, 1.51 (each s, 3H,
D
CH3), 3.37 (bs, 1H, OH), 3.99–4.21 (m, 2H, C4H2 interfered), 4.32–4.38 (m, 1H, C3H interfered), 4.42
(d, J=5.6 Hz, 1H, C2H).
(2S,3S)-12: [α]20=+9.43 (c 1.4, CHCl3), 82% de; 1H NMR (CDCl3): δ=1.40, 1.51 (each s, 3H, CH3),
D
3.23 (bs, 1H, OH), 4.02 (dd, J=5.1, 9.3 Hz, 1H, C4H2), 4.18 (dd, J=6.6 Hz, 1H, C4H2), 4.35 (dt, 1H,
C3H), 4.49 (d, J=4.5 Hz, 1H, C2H). MS (Auto CI, 70 eV) for C7H11NO3: calcd (MH+) 158.0817; found
158.0814. MS: m/z (%): 158.1 (1) [MH+], 142.1 (52) [M−CH3], 101.0 (29) [dioxolane], 43.0 (100), 28.0
(25).
5.9. Preparation of D-erythronic acid γ-lactone from (2S,3R)-12
A solution of (2S,3R)-12 (146 mg, 0.93 mmol) in conc. HCl (6 mL) was heated to 60°C for 3 h. The
reaction mixture was evaporated, and the residue was extracted three times with ethyl acetate (5 mL
each). The combined extracts were concentrated to give 77 mg (61%) D-erythronic acid γ-lactone.
Acknowledgements
This work was supported by the Bundesministerium für Bildung und Forschung (Zentrales Schwer-
punktprogramm Bioverfahrenstechnik, Stuttgart).
References
1. Enzyme-Catalyzed Reactions. Part 37. Part 36: Gaupp, S.; Effenberger, F. Tetrahedron: Asymmetry 1999, 10, 1777–1786.
2. (a) Kiliani, H. Ber. Dtsch. Chem. Ges. 1885, 18, 3066–3072. (b) Kiliani, H. Ber. Dtsch. Chem. Ges. 1887, 20, 339–346. (c)
Fischer, E. Ber. Dtsch. Chem. Ges. 1889, 22, 2204–2205.
3. (a) Effenberger, F. Angew. Chem., Int. Ed. Engl. 1994, 33, 1555–1564. (b) Brussee, J.; Dofferhoff, F.; Kruse, C. G.; van
der Gen, A. Tetrahedron 1990, 46, 1653–1658.
4. Forth, W.; Henschler, D.; Rummel, W. Pharmakologie und Toxikologie; 5th ed.; Wissenschaftsverlag: Mannheim, 1988.
5. Sham, H. L.; Rempel, C. A.; Stein, H.; Cohen, J. J. Chem. Soc., Chem. Commun. 1990, 666–667.
6. (a) Arcamone, F.; Franceschi, G.; Orezzi, P.; Cassinelli, G.; Barbieri, W.; Mondelli, R. J. Am. Chem. Soc. 1964, 86,
5334–5335. (b) Arcamone, F.; Cassinelli, G.; Orezzi, P.; Franceschi, G.; Mondelli, R. J. Am. Chem. Soc. 1964, 86,
5335–5336.
7. Effenberger, F.; Hopf, M.; Ziegler, T.; Hudelmayer, J. Chem. Ber. 1991, 124, 1651–1659.
8. (a) Hopf, M. Dissertation; Universität Stuttgart, 1990. (b) Althoff, W.; Karsdorf, R.; Tinapp, P. Arch. Pharm. 1981, 314,
518–524.
9. Matthews, B. R.; Gountzos, H.; Jackson, W. R.; Watson, K. G. Tetrahedron Lett. 1989, 30, 5157–5158.
10. (a) Reetz, M. T.; Kessler, K.; Jung, A. Angew. Chem., Int. Ed. Engl. 1985, 24, 989–990. (b) Reetz, M. T.; Fox, D. N. A.
Tetrahedron Lett. 1993, 34, 1119–1122. (c) Ipaktschi, J.; Heydari, A. Chem. Ber. 1993, 126, 1905–1912. (d) Gu, J.-H.;
Okamoto, M.; Terada, M.; Mikami, K.; Nakai, T. Chem. Lett. 1992, 1169–1172.
11. Brussee, J.; Loos, W. T.; Kruse, C. G.; van der Gen, A. Tetrahedron 1990, 46, 979–986.
12. Schmidt, M.; Hervé, S.; Klempier, N.; Griengl, H. Tetrahedron 1996, 52, 7833–7840.
13. (a) Jäger, J. Dissertation; Universität Stuttgart, 1996. (b) Effenberger, F.; Jäger, J. J. Org. Chem. 1997, 62, 3867–3873.