Synlett, Inhaltsverzeichnis Synlett 2025; 36(04): 329-334DOI: 10.1055/a-2364-6119 letter Thieme Chemistry Journals Awardees 2024 Phosphazene-Catalyzed Cascade Esterification/Stereoselective Aza-Michael Addition of Chiral β-Trifluoromethyl-α,β-unsaturated N-Acylated Oxazolidin-2-ones Authors Institutsangaben Sasirome Racochote a Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand Chutima Kuhakarn a Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand b Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand Pawaret Leowanawat a Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand b Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand Vichai Reutrakul a Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand b Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand Darunee Soorukram ∗ a Department of Chemistry, Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand b Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, Rama 6 Road, Bangkok 10400, Thailand Artikel empfehlen Abstract Artikel einzeln kaufen(opens in new window) Alle Artikel dieser Rubrik(opens in new window) Abstract Upon treatment of chiral β-trifluoromethyl-α,β-unsaturated N-acylated oxazolidin-2-ones with a range of alcohols using phosphazene base as a catalyst, the unexpected cascade esterification/stereoselective aza-Michael addition was observed. The reactions proceeded with high diastereoselectivities (up to >99:1) to give a series of enantioenriched aza-Michael addition products in good to high yields. The structure and stereochemistry of the representative aza-Michael adduct were confirmed by X-ray crystal structure analysis. The plausible mechanism was proposed on the basis of the experimental results.The synthetic transformations of chiral aza-Michael addition products were also demonstrated highlighting the synthetic application of the present work. Key words Key wordsaza-Michael addition - oxa-Michael addition - esterification - phosphazene - trifluoromethyl group - cascade reaction Volltext Referenzen References and Notes 1 Nie J, Guo H.-C, Cahard D, Ma J.-A. Chem. Rev. 2011; 111: 455 2a Hagmann WK. J. Med. Chem. 2008; 51: 4359 2b Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320 3a Besset T, Poisson T, Pannecoucke X. J. Fluorine Chem. 2015; 178: 225 3b Reznikov AN, Klimochkin YN. 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The combined organic layer was washed with a saturated aqueous NaCl solution (30 mL), brine, and dried over anhydrous Na2SO4. After removal of the solvent in vacuo, the residue was purified by column chromatography (70% CH2Cl2 in hexanes) to afford (S,R)-3a (60.1 mg, 75% yield, dr 97:3, 19F NMR analysis) as a white solid.Compound (S,R)-3a: Rf = 0.30 (70% CH2Cl2 in hexanes); mp 85–87 °C (70% CH2Cl2 in hexanes); [α]D 23 –31.5 (c 1.1, CHCl3). 1H NMR (400 MHz, CDCl3): δ = 7.43–7.31 (m, 8 H, ArH), 7.30–7.23 (m, 2 H, ArH), 5.15 (ABq, J = 12.1 Hz, 2 H, CHH), 4.75 (dd, J = 8.2, 8.2 Hz, 1 H, CHN), 4.50–4.38 (m, 2 H, CHHO, CH), 4.11 (dd, J = 7.6, 8.5 Hz, 1 H, CHHO), 3.21 (dd, J = 10.5, 16.6 Hz, 1 H, CHH), 2.86 (dd, J = 4.4, 16.6 Hz, 1 H, CHH). 13C NMR (100 MHz, CDCl3): δ = 168.6 (CO), 157.5 (CO), 136.4 (C), 135.2 (C), 129.6 (CH), 129.2 (2 × CH), 128.7 (2 × CH), 128.6 (CH), 128.5 (2 × CH), 127.7 (2 × CH), 124.4 (q, 1 JCF = 282.4 Hz, CF3), 70.5 (CH2), 67.3 (CH2), 59.9 (CH), 52.7 (q, 2 JCF = 32.2 Hz, CH), 30.4 (CH2). 19F NMR (376 MHz, CDCl3): δ = –72.4 (CF3). IR (ATR): λmax = 1757, 1496, 1479, 1361, 1243, 1184, 1124 cm–1. MS: m/z (%) relative intensity 394 [(M + H)+, 92], 286 (100), 216 (30), 91 (30). HRMS (ESI-TOF): m/z calcd for C20H18F3NO4Na+ [M + Na]+: 416.1080; found: 416.1082. 23 Katz SJ, Bergmeier SC. Tetrahedron Lett. 2002; 43: 557 ; see also ref. 19 24 Sun F, Van der Eycken EV, Feng H. Adv. Synth. Catal. 2021; 363: 5168 Zusatzmaterial Zusatzmaterial Supporting Information (PDF)
