Ru-MACHO-Catalyzed Highly Chemoselective Hydrogenation of α-Keto Esters to 1,2-Diols or α-Hydroxy Esters

Abstract

A ruthenium pincer catalyst has been shown to be highly effective for the hydrogenation of a wide range of α-keto esters, affording either diols or hydroxy esters depending on the choice of reaction conditions. Strong base, high temperature, and pressure favor the formation of diols whilst the opposite is true for the hydroxy esters.

Key words

hydrogenation - α-ketoesters - α-hydroxy esters - diols - ruthenium catalyst

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• 20 Typical Procedures for Hydrogenation of α-Keto Esters with Ru-MACHO A glass liner containing a stir bar was charged with substrate (0.5 mmol), base (0.05 mmol), Ru-MACHO (5 μmol) and MeOH (0.5 mL) in a glove box. The glass liner was then placed into an autoclave followed by degassing with H₂ three times. The hydrogenation was carried out at 10–50 bar H₂ with stirring at 80 °C for 12–24 h. After the reaction finished, the autoclave was allowed to cool down to r.t. The hydrogen gas was then carefully released in a fume hood, and the solution transferred to a flask with H₂O (2 mL), extracted with CH₂Cl₂ (3 × 5 mL), dried with Na₂SO₄, and concentrated in vacuo to afford the pure product 2a–s or 3a–s (see Supporting Information). Compound 2a: 91% yield, white solid; mp 56–58 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.28–7.38 (m, 5 H), 4.83 (dd, J = 3.6, 8.1 Hz, 1 H), 3.76–3.79 (m, 1 H), 3.65–3.70 (m, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 140.6, 128.7, 128.2, 126.2, 74.8, 68.2 ppm. MS (EI): m/z calcd for C₈H₁₀O₂ [M + Na]⁺: 161.0578; found: 161.0561. Compound 3a: 98% yield, colorless liquid. ¹H NMR (400 MHz, CDCl₃): δ = 7.33–7.43 (m, 1 H), 5.19 (s, 1 H), 3.75 (s, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 174.3, 138.3, 128.7, 128.7, 126.7, 73.0, 53.2 ppm. ESI-HRMS: m/z calcd for C₉H₁₀O₃ [M + Na]⁺: 189.0528; found: 189.0510.
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