Stereoselective Synthesis of (Z)-Allyl Alcohols through Coinage-Metal-Catalyzed Nucleophilic Addition of Benzo[d]isoxazoles with Unactivated Propargyl Alcohols

Abstract

The Au/Ag-cocatalyzed stereoselective addition reaction of cyanophenol anion species generated in situ with unactivated propargyl alcohols to produce functionalized (Z)-allyl alcohols in mostly good yields is reported. Benzo[d]isoxazoles were found to be excellent building blocks for the production of highly reactive cyanophenol anions from Kemp elimination reactions, thus serving as a masked benzonitrile source for the preparation of organonitrile derivatives. Silver salt combined with gold catalyst were found to be necessary for the success of this transformation.

Key words

transition-metal catalysis - Kemp elimination - stereoselective - benzo[d]isoxazole - allyl alcohol

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• 23 Representative Procedure for the Preparation of 3a: To a stirred solution of propargyl alcohol 1a (0.5 mmol) in anhydrous toluene (3.0 mL) was added Ph₃PAuCl (0.025 mmol), AgOAc (0.05 mmol) and Li₂CO₃ (0.5 mmol) at room temperature. The reaction was purged with N₂, and then benzo[d]isoxazole 2a (0.75 mmol) dissolved in toluene (1.0 mL) was added by using a syringe. The reaction was heated to 80 °C for ca. 4–6 h. After completion of the reaction as indicated by TLC, the reaction was allowed to cool to room temperature, diluted with ethyl acetate (5.0 mL), and extracted. The combined organic phase was washed with brine, dried over Na₂SO₄, and concentrated to give the crude residue, which was purified by silica column chromatography (elute: PE/EtOAc = 20:1 v/v) to give the desired product 3a. Yield: 135 mg (79%); yellow solid; mp 105–106 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.54–7.51 (m, 1 H), 7.41–7.36 (m, 2 H), 7.24–7.16 (m, 6 H), 7.04 (d, J = 7.6 Hz, 2 H), 6.92 (t, J = 7.6 Hz, 1 H), 6.69 (d, J = 8.8 Hz, 1 H), 6.04 (d, J = 8.8 Hz, 1 H), 5.60 (d, J = 8.4 Hz, 1 H), 2.24 (br, 1 H), 2.23 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 158.8, 148.8, 139.8, 137.6, 134.3, 133.9, 133.5, 133.4, 129.3, 128.8, 125.9, 122.3, 121.1, 116.1, 115.5, 102.2, 68.9, 21.1. HRMS: m/z [M + H]⁺ calcd for C₂₃H₂₀NO₂: 342.1489; found: 342.1487.
• 24 Representative Procedure for the Preparation of 4: A mixture of 3a (0.30 mmol), K₂CO₃ (0.45 mmol), and H₂O₂ (0.60 mmol) in DMSO (1.5 mL) was stirred at room temperature overnight. TLC was used to monitor the reaction until completion. Water (10 mL) was added, and the resulting mixture was extracted with ethyl acetate (3 × 10 mL). The combined organic solution was washed with brine, dried over MgSO₄, and concentrated. The crude product was purified by silica gel column chromatography (PE/EtOAc = 2:1 v/v) to give the product 4. Yield: 72 mg (67%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 8.15–8.12 (m, 1 H), 7.66 (s, 1 H), 7.35 (br, 2 H), 7.22–7.09 (m, 6 H), 7.07–7.00 (m, 2 H), 6.98–6.96 (m, 1 H), 6.71 (d, J = 8.2 Hz, 1 H), 6.15 (d, J = 8.4 Hz, 1 H), 6.08 (d, J = 7.0 Hz, 1 H), 5.52 (d, J = 8.4 Hz, 1 H), 2.29 (br, 1 H), 2.24 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 166.7, 155.2, 148.4, 140.0, 137.8, 136.4, 133.4, 132.7, 129.4, 129.2, 128.8, 128.7, 126.1, 125.6, 122.5, 121.0, 115.1, 69.1, 21.1. HRMS: m/z [M + H]⁺ calcd for C₂₃H₂₂NO₃: 360.1594; found: 360.1587.