16
T. Hirata et al. / Tetrahedron: Asymmetry 15 (2004) 15–16
Table 1. Hydrogenation of maleimides by the cultured cells of higher plants
Substrates
Products
Cultured cells
Reaction time (day)
Conversion (%)a
Ee (%)b
Configuration
1
4
N. tabacum
C. roseus
5
5
5
5
5
1
5
1
49
19
––
––
––
––
––
––
––
99
––
––
––
––
––
––
––
R
2
3
5
6
N. tabacum
C. roseus
84
86
N. tabacum
N. tabacum
C. roseus
>99
>99
>99
>99
7
8
N. tabacum
a The conversions expressed as a percentage of the products in the reaction mixture on the basis of GLC analysis.
b The enantiomeric excess was calculated on the peak analysis of the 1H NMR of the product with chiral shift reagent, Eu(hfc)3.
(MS) medium5 supplemented with 3% sucrose and 10 mM
of 2,4-dichlorophenoxyacetic acid (2,4-D) under illumina-
tion (4000 lux). On the other hand, suspension cells of C.
roseus6 were cultured in 500 mL conical flasks containing
200 mL of SH medium,7 supplemented with 3% sucrose
and 10 mM 2,4-D under illumination (4000 lux). Each
suspension cell was cultivated on a rotary shaker (75 rpm)
at 25 °C for 3weeks prior to use for biotransformation
experiments.
of the C–C double bond of the maleimide hence pro-
ducing an optically active 2-substituted succinimide. It is
worthy of note that the enantiofacially selective hydro-
genation of 2-alkylated maleimide derivatives using
cultured plant cells as biocatalysts is one of the more
useful methods for chiral generation. The investigation
of the enzymes, which catalyze such an asymmetric
hydrogenation in N. tabacum is currently in progress.
4. Hirata, T.; Aoki, T.; Hirano, Y.; Ito, T.; Suga, T. Bull.
Chem. Soc. Jpn. 1981, 54, 3527.
5. Murashige, T.; Skoog, F. Physiol. Plant. 1962, 15,
473.
References and Notes
6. Hamada, H.; Fuchikami, Y.; Ikematsu, Y.; Hirata, T.;
Williams, H.; Scott, A. I. Phytochemistry 1994, 37, 1037.
7. Schenk, R. U.; Hildebrand, A. C. Can. J. Botany 1972, 50,
199.
1. For example: (a) Matsumoto, K.; Tsutsumi, S.; Ihori, T.;
Ohta, H. J. Am. Chem. Soc. 1990, 112, 9614; (b) Fujii, I.;
Lerner, R. A.; Janda, K. D. J. Am. Chem. Soc. 1991, 113,
8528; (c) Henin, F.; Muzart, J. Tetrahedron: Asymmetry
1992, 9, 1161; (d) Yasukata, T.; Koga, K. Tetrahedron:
Asymmetry 1993, 4, 35; (e) Fuji, K.; Tanaka, K.; Miya-
moto, H. Tetrahedron: Asymmetry 1993, 4, 247; (f) Cave-
lier, F.; Gomez, S.; Jacquier, R.; Verducci, J. Tetrahedron:
Asymmetry 1993, 4, 2501; (g) Ishihara, K.; Kaneeda, M.;
Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 11179; (h)
Cavelier, F.; Gomez, S.; Jacquier, R.; Verducci, J. Tetra-
hedron Lett. 1994, 35, 2891; (i) Fuji, K.; Kawabata, T.;
Kuroda, A. J. Org. Chem. 1995, 60, 1914; (j) Piva, O. J.
Org. Chem. 1995, 60, 7879; (k) Takahashi, T.; Nakao, N.;
Koizumi, T. Chem. Lett. 1996, 207; (l) Kataoka, M.;
Kotaka, A.; Hasegawa, A.; Wada, M.; Yoshizumi, A.;
Nakamori, S.; Shimizu, S. Biosci. Biotechnol. Biochem.
2002, 66, 2651.
25
22
8. Product 8: ½a +6.6 (c 0.56, CHCl3) {lit9 ½a +8 (c 1.2,
D
D
CHCl3) for (R)-enantiomer}; IR (in CHCl3) 1712 cmÀ1
(C@O); CD (c 0.52, CHCl3) ½h )76.9; 1H NMR
(500 MHz, CDCl3) d 1.46 (3H, d, J ¼ 7:1 Hz, 2-Me),
3.04 (1H, ddq, J ¼ 9:3, 4.6, and 7.3 Hz, 2-H), 2.51 (1H, dd,
J ¼ 17:7 and 4.5 Hz, 3-Ha), 3.10 (1H, dd, J ¼ 17:6 and
9.3Hz, 3-Hb), 7.29 (2H, d, J ¼ 8:3Hz, o-H), 7.39 (1H, t,
J ¼ 7:4 Hz, p-H), 7.47 (2H, t, J ¼ 7:7 Hz, m-H); 13C NMR
(125 MHz, CDCl3) d 16.9 (Me), 34.9 (CH), 36.7 (CH2),
126.4 (o-C in Ph), 128.6 (p-C in Ph), 129.1 (m-C in Ph),
132.0 (N–C in Ph), 175.4 (C@O), 179.5 (C@O).
9. Balenovic, K.; Bregant, N. J. Chem. Soc. 1965, 5131.
10. Methyl proton signals of racemic N-phenyl-2-methylsuc-
cinimide in the 1H NMR spectrum were revealed at d 2.64
(d, J ¼ 7:0 Hz; relative integral value ¼ 100) and 2.56 (d,
J ¼ 7:0 Hz; integral value ¼ 100) in a CDCl3 solution of
the sample and Eu(hfc)3 (1:1 mol ratio). On the other
hand, the 1H NMR of the product 8 under the same
conditions showed the methyl proton signals at d 2.64 (d,
J ¼ 7:0 Hz; integral value ¼ 0.55) and 2.56 (d, J ¼ 7:0 Hz;
integral value ¼ 100).
2. (a) Hirata, T.; Shimoda, S.; Gondai, T. Chem. Lett. 2000,
850; (b) Shimoda, K.; Izumi, S.; Hirata, T. Bull. Chem.
Soc. Jpn. 2002, 75, 813.
3. Suspension cells of N. tabacum4 were cultured in 500 mL
conical flasks containing 200 mL Murashige and SkoogÕs