Highly Enantio- and Diastereoselective l-Proline Derived Acetylglucose Amide Catalyzed Aldol Reaction of Ketones to Aldehydes under Solvent-Free Conditions

Abstract

A novel organocatalyst was developed from d-glucosamine and l-proline, which was shown to catalyze the direct aldol reaction of ketones with aldehydes in a highly diastereoselective and enantioselective manner under solvent-free conditions. The presence of 10 mol% catalyst could promote the reaction effectively, affording the desired aldol products in high yields (70–99%) and excellent selectivities (up to >99:1 dr and up to >99% ee).

Key words

organocatalyst - stereoselectivity - enantioselectivity - aldol reaction - solvent-free

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• 9 Catalytic Asymmetric Aldol Reaction; Typical Procedure: Cyclohexanone (0.2 mmol, 2.0 equiv), aldehyde (0.1 mmol, 1.0 equiv), and catalyst 1 (0.01 mmol, 10 mol%) were mixed together at room temperature. The mixture was stirred at room temperature until the aldehyde was consumed (reaction monitored by TLC). The mixture was diluted with CH₂Cl₂ (0.5 mL), and then purified directly by column chromatography on silica gel to give the desired optically active aldol product. Analytical data of compound 4b are given as a representative compound (see the Supporting Information data on all products). Yield: 0.0241 g (96%); yellow solid; [α] _d ²⁰ –29 (c = 1.0, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 8.22–8.16 (m, 2 H), 7.68 (d, J = 7.4 Hz, 1 H), 7.55 (d, J = 7.4 Hz, 1 H), 4.91 (dd, J = 2.7, 8.2 Hz, 1 H), 4.15 (d, J = 2.8 Hz, 1 H), 2.66–2.62 (m, 1 H), 2.53–2.38 (m, 2 H), 2.14–2.11 (m, 1 H), 1.86–1.57 (m, 3 H), 1.42–1.38 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 215.0, 148.3, 143.2, 133.2, 129.3, 122.9, 122.0, 74.0, 57.1, 42.7, 30.7, 27.6, 24.6. HRMS: m/z [M⁺] calcd for C₁₃H₁₅NO₄: 249.1001; found: 249.1099.