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Synlett 2025; 36(04): 329-334
DOI: 10.1055/a-2364-6119
DOI: 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
This project is funded by National Research Council of Thailand (NRCT) and Mahidol University (N42A650346). A student scholarship to S.R. from the Science Achievement Scholarship of Thailand (SAST) is gratefully acknowledged.
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
aza-Michael addition - oxa-Michael addition - esterification - phosphazene - trifluoromethyl group - cascade reactionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2364-6119.
- Supporting Information
Publication History
Received: 12 June 2024
Accepted after revision: 16 July 2024
Accepted Manuscript online:
16 July 2024
Article published online:
05 August 2024
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- 22 Cascade Esterification/Stereoselective aza-Michael Addition Reaction of 1aA flame-dried round-bottom flask equipped with a magnetic stirring bar, an argon inlet, and a rubber septum was charged with 1a (58.3 mg, 0.20 mmol), benzyl alcohol (2a, 24 μL, 0.22 mmol), and dry MeCN (1 mL). The resulting solution was cooled at 0 °C then P2-t-Bu solution (2.0 M in THF, 10 μL, 0.02 mmol) was added. After stirring at 0 °C for 6 h, the reaction mixture was quenched with 10% HCl solution (10 mL) and extracted with EtOAc (3 × 20 mL). 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.
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For oxa-Michael addition, see: