Highly Diastereoselective Synthesis of 3-Indolyl-N-Substituted Glycine Derivatives via TFA-Promoted Friedel-Crafts Type Reaction of Indoles with Chiral Cyclic Glyoxylate Imine

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.

Friedel-Crafts reaction - Brönsted acid - chiral cyclic glyoxylate imines - optically active indolyglycines

References

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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.

<A NAME="RU05403ST-19">19</A>

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 ų, Z = 4; D _calcd = 1.293 g/cm³; F ₀ = 528; number of reflections measured = 2737, l = 0.7107 Å.

<A NAME="RU05403ST-20">20</A>

X-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 ų, Z = 4; D _calcd = 1.426 g/cm³; F ₀ = 912; number of reflections measured = 4268, l = 0.7107 Å.

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Several methods have existed for the removal of the chiral template from the similar compounds without notable racemization:

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<A NAME="RU05403ST-22D">22d</A>

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).