Chemo-, Regio-, and Stereoselective Synthesis of syn-Aryl Glycol Monoesters from Aryl Olefins with Hydrogen Peroxide Catalyzed by RuCl₃

Abstract

Chemo-, regio-, and stereoselectivity have been achieved in the oxidations of aryl olefins. The aryl olefins were oxidized by 2 equivalents of H₂O₂ in acetic acid, catalyzed by 0.02 equivalent of RuCl₃, leading to the formations of syn-aryl glycol monoesters. As the reaction is concerted, both the regio- and stereo­selectivity are excellent. In the presence of aliphatic C=C bonds, the aryl C=C bonds were selectively dioxygenated. This represents the first example of chemoselective dioxygenation of aryl C=C bonds.

Key words

synthetic methods - oxidation - glycol monoesters - olefins - hydrogen peroxide

References and Notes

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12

General Procedure for the Oxidation of Aryl Olefins
To a solution of olefin (1 mmol) and RuCl₃˙nH₂O (0.02 mmol) in AcOH (20 mL) was added H₂O₂ (30%, 2 mmol) in AcOH (5 mL) dropwisely at r.t. When all H₂O₂ was added in 15 min, the reaction was completed as checked by TLC. The reaction mixture was diluted with H₂O (100 mL), and extracted with EtOAc (3 × 30 mL). The organic layers were combined, neutralized with aq NaHCO₃ (3 × 30 mL), washed with brine (3 × 30 mL), dried over anhyd Na₂SO₄, and concentrated in vacuum to give the crude product which was purified by flash chromatography on silica gel to afford the corresponding product, the aryl glycol monoester (for details: Table  [¹] and Supporting Information). Spectroscopic Data for a Product (Entry 27, Table 1) White solid (mp 248-250 ˚C); yield 50%. IR (KBr): ν = 3436, 2935, 2814, 1731, 1675, 1546, 1218, 1034 cm^-¹. ^¹H NMR (500 MHz, DMSO-d ₆): δ = 7.34-7.04 (m, 12 H), 6.18 (m, 2 H), 6.14 (d, J = 5.5 Hz, 1 H), 5.79 (d, J = 6.5 Hz, 1 H), 5.33 (d, J = 4.9 Hz, 1 H), 4.01 (dd, J = 7.0, 14.1 Hz, 1 H), 3.46 (m, 2 H), 3.30 (m, 2 H), 2.22 (s, 3 H), 2.00 (s, 3 H), 1.56 (m, 2 H) ppm. ^¹³C NMR (125 MHz, DMSO-d ₆): δ = 177.16, 177.14, 170.65, 137.57, 136.67, 136.11, 135.20, 134.26, 129.48, 129.32, 128.83, 128.54, 127.37, 127.01, 126.76, 126.14, 71.70, 62.55, 60.47, 52.41, 46.12, 45.50, 21.41, 21.25 ppm. ESI-MS: m/z = 585.2 [M + Na]⁺. ESI-HRMS: m/z calcd for C₃₄H₃₀N₂O₆ + Na [M + Na]⁺: 585.2001; found: 585.2009.