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DOI: 10.1055/s-2003-39905
Highly Diastereoselective Synthesis of 3-Indolyl-N-Substituted Glycine Derivatives via TFA-Promoted Friedel-Crafts Type Reaction of Indoles with Chiral Cyclic Glyoxylate Imine
Publikationsverlauf
Publikationsdatum:
11. Juni 2003 (online)

Abstract
A method based on the highly diastereoselective Friedel-Crafts type reaction of indoles with chiral cyclic glyoxylate imines in the presence of TFA toward the stereoselective synthesis of 3-indolyl-N-substituted glycine derivatives is presented. The absolute configuration of the newly formed chiral center was determined by a single-crystal X-ray analysis.
Key words
Friedel-Crafts reaction - Brönsted acid - chiral cyclic glyoxylate imines - optically active indolyglycines
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Although we did not study this issue systematically, the preliminary result showed that when 3bc was subjected to the hydrogenolysis in aqueous methanol using Pearlman’s catalyst [Pd(OH)2/C] and TFA under 1 atmosphere of hydrogen gas for 5 h, the corresponding optically active amino acid was obtained in 82% yield, [α]D 20 +57 (c 0.35, CH3OH).
References
Representative experimental procedure:
To a solution of indole (1.2 equiv) and chiral cyclic glyoxylate
imine (1.0 equiv) in CH2Cl2 at 0 °C,
TFA (5 equiv) was added dropwise by syringe. After the reaction
mixture was stirred for 3 h at 0 °C, usual work-up furnished
a residue from which the pure product was obtained after purification
with flash chromatography on silica gel [all new compounds
were subjected to 1H NMR, 13C
NMR, IR, MS(FAB) analysis]. The diastereoselectivity was
determined by 1H NMR and 13C NMR
spectra. All compounds gave satisfactory spectral data. Selected
data for compound 3c*: mp: 234-236 °C, [α]D
20 +148.57
(c 0.7, acetone); FTIR (KBr) 3338, 1734, 1693,
1538, 1454, 1377, 1343, 1319, 1256, 1217, 1190, 1086, 1014 cm-1; 1H
NMR(300 Hz, CDCl3): δ 1.38 (t, J = 7 Hz
3 H), 2.54 (br s, 1 H), 4.43 (m, 2 H), 4.90 (d, J = 4
Hz,
1 H), 5.90 (s, 1 H), 6.14 (d, J = 4
Hz, 1 H), 7.11-7.29 (m, 12 H), 7.39-7.45 (m, 2
H), 7.79 (d, J = 8 Hz, 1 H),
8.96 (br s,
1 H); 13C NMR(75
Hz, CDCl3) δ 14.5, 52.8, 58.3, 61.6, 85.4, 113.4,
121.4, 121.8, 125.7, 126.0, 127.6, 128.2, 128.4, 128.6, 128.9, 129.3,
137.2, 138.0, 138.5, 162.3, 169.3; HRMS (FAB): m/z 441.1811
for [MH+] C27H25N2O4 requires
441.1808.
X-Ray analysis of 2c: The crystal used for the X-ray study had the dimensions 0.29 × 0.17 × 0.08 mm. Crystal data: C16H13NO2, M 251.27; orthorhombic; space group, P21; lattice parameters, a = 5.9439 Å, b = 8.4943 Å, c = 25.5719 Å; V = 1291.11 Å3, Z = 4; D calcd = 1.293 g/cm3; F 0 = 528; number of reflections measured = 2737, l = 0.7107 Å.
20X-Ray analysis of 3hc: The crystal used for the X-ray study had the dimensions 0.53 × 0.09 × 0.04 mm. Crystal data: C24H19BrN2O2, M 447.32; Monoclinic; space group, C2; lattice parameters, a = 26.817 Å, b = 7.9070 Å, c = 9.8754 Å; V = 2083.1 Å3, Z = 4; D calcd = 1.426 g/cm3; F 0 = 912; number of reflections measured = 4268, l = 0.7107 Å.