Asymmetric Epoxidation of Enones by Peptide-Based Catalyst: A Strategy Inverting Juliá–Colonna Stereoselectivity

Abstract

A resin-supported peptide catalyst with an N-terminal primary amino group was developed for asymmetric epoxidation of enones through iminium activation. The peptide has N-terminal l-3-(1-pyrenyl)alanine, a non-natural amino acid with a bulky side chain, which is connected to l-proline and then to 3₁₀-helical (l-Leu-l-Leu-Aib)₂ (Aib: 2-aminoisobutyric acid). This peptide successfully catalyzed the asymmetric epoxidation of β-aryl-substituted enones with electron-withdrawing groups on the aryl group. The feature of the present peptide catalyst is that the sense of the enantioselectivity is opposite to that of Juliá–Colonna reaction, oligo-l-Leu-catalyzed epoxidation of enones, while both of the peptide catalysts consist of l-amino acids.

Key words

peptide - asymmetric catalysis - epoxidation - organocatalysis - immobilized catalyst

• References and Notes


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• 23 Such a deactivation of the catalyst hampered the reuse of the catalyst even under optimum conditions.
• 24 When the R¹ group of substrate 2 was 4-methoxyphenyl, epoxidation did not proceed.
• 25 Typical Procedure for Peptide-Catalyzed Epoxidation Water (200 μL) was added slowly with stirring to a round-bottom flask that contained enone 2f (0.03 mmol), resin-supported Ala(1-Pyn)-Pro-(Leu-Leu-Aib)₂ (54 mg, 0.012 mmol of the N-terminal amino group), benzoic acid (0.006 mmol), and THF (100 μL). UHP (1.5 mmol) was added, and the flask was warmed to 40 °C. After stirring the mixture for 48 h, an aq sat. solution of NH₄Cl was added. The resulting mixture was stirred for 5 min, and peptide catalyst was filtered off and washed with CHCl₃. The filtrate solution was extracted with CHCl₃, and the organic layer was dried over anhydrous MgSO₄. After the removal of the solvent under reduced pressure, the residue was purified by preparative TLC (hexanes–EtOAc, 2:1) to afford epoxy ketone 3f. The amounts of the catalyst and benzoic acid, and the reaction time varied depending on a substrate (see the footnotes of Table 2)
• 26 Characterization Data of Epoxy Ketones (3S,4R)-Epoxy-4-(3,5-dichlorophenyl)butan-2-one (3f) ¹H NMR (400 MHz, CDCl₃): δ = 7.35 (t, J = 1.8 Hz, 1 H), 7.17 (d, J = 1.8 Hz, 2 H), 3.97 (d, J = 1.8 Hz, 1 H), 3.43 (d, J = 1.8 Hz, 1 H), 2.20 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 203.09, 138.60, 135.54, 129.16, 124.16, 63.03, 56.31, 24.96. HRMS–FAB: m/z calcd for C₁₀H₉Cl₂O₂ [M + H]⁺: 230.9979; found: 230.9979. The ee was determined by HPLC analysis (Chiralcel OJ-H; hexane–2-PrOH, 95:5; 1.0 mL min^–1): t _R (major) = 20.3 min; t _R (minor) = 22.1 min. (1R,2S)-Epoxy-1-(2,4-dinitrophenyl)pentan-3-one (3i) ¹H NMR (400 MHz, CDCl₃): δ = 9.06 (d, J = 2.3 Hz, 1 H), 8.55 (dd, J = 8.7, 2.3 Hz, 1 H), 7.88 (d, J = 8.7 Hz, 1 H), 4.65 (d, J = 2.1 Hz, 1 H), 3.47 (d, J = 2.1 Hz, 1 H), 2.63 (dt, J = 17.4, 7.3 Hz, 1 H), 2.53 (dt, J = 17.4, 7.3 Hz, 1 H), 1.73 (sext, J = 7.3 Hz, 2 H), 1.00 (t, J = 7.3 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 203.58, 147.84, 147.45, 138.83, 128.96, 128.64, 120.53, 61.28, 55.83, 40.23, 16.55, 13.62. HRMS–FAB: m/z calcd for C₁₂H₁₃N₂O₆ [M + H]⁺: 281.0773; found: 281.0770. The ee was determined by HPLC analysis (Chiralcel OD-H; hexane–2-PrOH, 70:30; 0.8 mL min^–1): t _R (major) = 29.9 min; t _R (minor) = 43.5 min.