Synlett 2016; 27(08): 1217-1222
DOI: 10.1055/s-0035-1560597
cluster
© Georg Thieme Verlag Stuttgart · New York

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

Kengo Akagawa
Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan   Email: kkudo@iis.u-tokyo.ac.jp
,
Tomoaki Hirata
Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan   Email: kkudo@iis.u-tokyo.ac.jp
,
Kazuaki Kudo*
Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan   Email: kkudo@iis.u-tokyo.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 04 October 2015

Accepted after revision: 08 November 2015

Publication Date:
23 December 2015 (online)

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.

Supporting Information

 
  • 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.