Enantioselective Allyl-, and Allenylboration of Aldehydes Catalyzed by Chiral Hydroxyl Carboxylic Acid

Abstract

Asymmetric allylboration of aldehydes with allylboronic acid pinacol ester catalyzed by chiral hydroxyl carboxylic acid is described. This reaction provides synthetically useful homoallyl alcohols in high yield with good to high enantioselectivity. The present catalytic protocol was also examined in asymmetric allenylboration of aldehydes at elevated temperature to afford chiral homopropargyl alcohols with reasonable asymmetric induction.

Key words

Brønsted acid catalysis - chiral hydroxyl carboxylic acid - allylboration - homoallyl alcohol - allenylboration - homopropargyl alcohol

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• 14 General Procedure: To a flame-dried glass tube equipped with a three-way top were placed chiral acid catalyst 2d (12.3 mg, 0.010 mmol), freshly distilled benzaldehyde (5a; 10 μL, 0.10 mmol), and anhydrous CH₂Cl₂ (0.5 mL) under Ar atmosphere. The resulting solution was cooled at –78 °C before allylboronic acid pinacol ester (6a; 37 μL, 0.20 mmol) was added by using a gas-tight syringe with a stainless steel needle. The reaction mixture was stirred at the same temperature for 5 h. The reaction was quenched with DIBAL-H (1.0 M in toluene, 15 μL). After stirring for 10 min, 4 M HCl was added to the mixture and the aqueous layer was extracted with CH₂Cl₂. The combined organic layers were washed with brine and dried over Na₂SO₄. After evaporation of the solvent under reduced pressure, the reaction mixture was purified by flash chromatography (EtOAc/hexanes, 1:9) to give 7a (11.0 mg, 74%) as a colorless oil; [α]_D ²⁹ –56.3 (c 0.72, CHCl₃, 85% ee sample). ¹H NMR (CDCl₃): δ = 7.37–7.25 (m, 5 H), 5.82 (dddd, J = 17.2, 10.3, 7.5, 6.9 Hz, 1 H), 5.21–5.13 (m, 2 H), 4.75 (t, J = 6.3 Hz, 1 H), 2.57–2.47 (m, 2 H), 2.03 (br s, 1 H). ¹³C NMR (CDCl₃): δ = 143.9, 134.4, 128.4, 127.5, 125.8, 118.4, 73.3, 43.8. CHIRALCEL OD-H (ϕ 0.46 cm × 25 cm; 2-propanol/n-hexane, 5:95; flow rate 0.5 mL/min, detection at 210 nm; t_R = 14.5 (R), 16.6 (S) min.

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