Carbene-Catalyzed Regioselective Addition of Oxindoles to Ynals for Quick Access to Allenes

Abstract

A catalytic regioselective addition reaction of oxindoles with ynals is developed. Allene-containing derivatives bearing various substituents and substitution patterns are afforded as the products in generally moderate to good yields with moderate diastereoselectivities. Several of allenes obtained from this protocol are valuable in the development of novel bactericides for plant protection.

Key words

N-heterocyclic carbene - regioselective addition - allene - organocatalysis - plant protection

• References and Notes

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• 16 General Procedure for Synthesizing Allenes Under nitrogen atmosphere, 1 (0.10 mmol), 2 (0.10 mmol), pre-NHC (0.02 mmol), base (0.05 mmol), DQ (0.12 mmol), and 4Å MS (100 mg) was dissolved in anhydrous THF (1 mL), then i-PrOH (100 μL) was added. The reaction mixture was allowed to stir for 5 h at room temperature. Then the mixture was concentrated under reduced pressure. The resulting crude residue was purified by column chromatography on silica gel to afford the desired product. Analytical Data of 3a ¹H NMR (400 MHz, CDCl₃): δ = 7.82 (d, J = 8.2 Hz, 1 H), 7.45–7.19 (m, 6 H), 6.98 (t, J = 7.6 Hz, 1 H), 6.68 (d, J = 7.6 Hz, 1 H), 6.15 (s, 1 H), 5.11–4.90 (m, 1 H), 4.54 (d, J = 22.8 Hz, 1 H), 3.70 (s, 3 H), 1.60 (s, 9 H), 1.19 (dd, J = 10.3, 6.3 Hz, 6 H). ¹³C NMR (101 MHz, CDCl₃): δ = 219.8, 169.4 (d, J = 22.1 Hz), 165.0, 163.0, 148.5, 140.0 (d, J = 5.4 Hz), 134.1, 131.6 (d, J = 2.7 Hz), 130.5, 128.3, 128.0, 125.7, 124.3 (d, J = 2.6 Hz), 123.6 (d, J = 18.6 Hz), 115.1, 101.3 (d, J = 2.5 Hz), 94.9, 92.6 (d, J = 199.2 Hz), 84.8, 69.0, 53.0, 50.1 (d, J = 25.5 Hz), 28.0, 21.7 (d, J = 3.3 Hz). ¹⁹F NMR (377 MHz, CDCl₃): δ = –158.2. HRMS (ESI): m/z calcd for C₂₉H₃₀F₂NO₇Na⁺ [M + Na]⁺: 546.1899; found: 546.1893. See the Supporting Information for full details and graphical guide.
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