Amino Acid Salt Catalyzed Asymmetric Synthesis of 1,2-Diols with A Quaternary Carbon Center

Abstract

Enantioenriched 1,2-diols with a quaternary carbon center have great potential in the preparation of natural and biologically active compounds, but remain challenging synthetic targets which demand for both good diastereo- and enantioselectivity. As part of our continuous effort to explore the unique catalytic activities of amino acid salts in the asymmetric synthesis, herein, we wish to report an amino acid salt catalyzed direct aldol reaction between hydroxyacetone and α-keto e­sters, which afforded the 1,2-diols with a quaternary carbon center in high diastereo- and enantioselectivities.

Key words

1,2-diols - quaternary carbon center - amino acid salts - asymmetric catalysis

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• 9 General Experimental Procedures for the Synthesis of 4 α-Keto esters 3 (0.2 mmol), catalyst 1h (20 mol%), and dry DMF (0.5 mL) were added to a tube. The mixture was stirred at –10 °C for 10 min, then hydroxyacetone (2, 1 mmol) was added dropwise, and the resulting mixture was stirred at this temperature for specific time until the reaction was completed. The reaction mixture was purified through flash column chromatography on a silica gel (eluent: PE–EtOAc = 10:1 to 5:1) to yield the targeting products. Data of Compound 4e C₁₅H₂₀O₅, 43.3 mg, 77% yield, white solid, 92% ee, 25:1 dr; [α]_D ²¹ –0.8 (c 0.33 in CH₂Cl₂). HPLC: DAICEL CHIRALCEL AD-H, 2-PrOH–n-hexane= 15:85, flow rate = 1.0 mL/min, λ = 254 nm, t _R (minor) = 8.8 min; t _R (major) = 10.6 min. ¹HNMR (500 MHz, CDCl₃): δ = 7.80–7.82 (m, 2 H), 7.40–7.43 (m, 2 H), 7.34–7.37 (m, 1 H), 4.88 (d, J = 5 Hz, 1 H), 4.08–4.10 (m, 2 H), 1.58 (s, 3 H), 1.50 (s, 9 H). ¹³CNMR (126 MHz, CDCl₃): δ = 27.8, 27.9, 80.2, 81.9, 84.4, 126.3, 128.4, 128.5, 137.9, 171.4, 205.2. IR (KBr): γ = 3497, 2974, 2352, 1716, 1252, 1162, 844, 751, 735, 700, 650 cm^–1. HRMS (Micromass GCT–MS ESI): m/z calcd for [C₁₅H₂₀NaO₅]⁺: 303.1208; found: 303.1217.