In Situ Electrophilic Activation of Hydrogen Peroxide for Catalytic Asymmetric α-Hydroxylation of 3-Substituted Oxindoles

Abstract

Peroxy trichloroacetimidic acid, in situ generated from aqueous hydrogen peroxide and trichloroacetonitrile, was found to act as a competent electrophilic oxygenating agent for the direct α-hydroxylation of oxindoles. The use of chiral 1,2,3-triazolium salt as a phase-transfer catalyst enabled rigorous absolute stereocontrol in the carbon–oxygen bond-forming reaction. The present study provides a new, yet practical method for straightforward access to optically active α-hydroxycarbonyl compounds.

Key words

hydroxylation - carbonyl compound - hydrogen peroxide - imidic acid - oxindole - chiral ion pair - 1,2,3-triazolium ion

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• 16 In the present system, the N-Boc group on the oxindole nitrogen seemed crucial for achieving high efficiency and enantioselectivity. For instance, attempted reaction of N-4-methoxyphenyl 3-phenyloxindole under identical conditions described in Table 2 afforded the corresponding α-hydroxyoxindole in moderate yield with low enantioselectivity (45% yield, 28% ee).
• 17 Representative Procedure for Catalytic Asymmetric α-Hydroxylation of Oxindoles A solution of 1c·Br (3.76 mg, 0.005 mmol), oxindole 2a (30.9 mg, 0.10 mmol), and K₂CO₃ (13.8 mg, 0.10 mmol) in Et₂O (1.0 mL) was degassed by alternating vacuum evacuation/argon backfill. Then, the resulting mixture was cooled to –10 °C. To this solution were successively added a 30% aq solution of H₂O₂ (50 μL, 0.50 mmol) and trichloroacetonitirile (10 μL, 0.10 mmol), and the mixture was stirred for 24 h. The reaction was quenched with a sat. aq solution of NH₄Cl, and the extractive workup was performed with EtOAc. The organic extracts were dried over Na₂SO₄, filtered, and concentrated. The crude residue was purified by column chromatography on silica gel (hexane–CHCl₃ = 3:1 as eluent) to afford 3a (31.5 mg, 0.097 mmol, 97% yield, 94% ee). Compound 3a: [α]_D ²³ = +45.6 (c = 3.0, CHCl₃) for 94% ee. ¹H NMR (400 MHz, CDCl₃): δ = 7.94 (1 H, d, J = 8.2 Hz), 7.40 (1 H, td, J = 8.0, 1.2 Hz), 7.36–7.29 (6 H, m), 7.20 (1 H, t, J = 7.8 Hz), 3.42 (1 H, s), 1.63 (9 H, s). ¹³C NMR (101 MHz, CDCl₃): δ = 176.0, 149.2, 139.9, 139.8, 130.3, 128.8, 128.7, 125.7, 125.4, 125.2, 115.6, 85.0, 77.8, 28.2, one peak for aromatic carbon was not found probably due to overlapping. IR (film): 3456, 3001, 2978, 1788, 1609, 1479, 1342, 1285, 1146, 908, 719 cm^-1. HRMS (ESI⁺): m/z calcd for C₁₉H₁₉NO₄Na⁺ [M + Na]⁺: 348.1206; found: 348.1206. HPLC (ID3, hexane–i-PrOH = 10:1, flow rate = 0.5 mL/min, λ = 210 nm): t = 15.8 min (major isomer); 17.5 min (minor isomer).