Highly Efficient Direct Allylation of Oxindoles with Simple Allylic Alcohols Enabled by Palladium/Brønsted Acid Catalysis

Abstract

A highly efficient and practical direct allylic alkylation of oxindoles with simple allylic alcohols cocatalyzed by Pd(OAc)₂/Ph₃P and PhCO₂H under mild conditions has been developed, which streamlines the installation of an all-carbon quaternary allylic center at the oxindole 3-position. Enantioselective allylic alkylation has also been realized with the product in almost quantitative yield and 17% enantiomeric excess. Mechanistically, ESI analysis indicates that a palladium(0) species and π-allyl-Pd(PPh₃)₂ cation were involved.

Key words

oxindole - allylic alkylation - Brønsted acids - allylic alcohol - palladium

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• 21 Typical Procedure To a flame-dried Schlenk tube charged with 4 Å MS (50 mg/0.1 mmol) and a magnetic stir bar was added 3-aryloxindoles 1 (0.1 mmol), allylic alcohol 2 (0.2 mmol), Pd(OAc)₂ (3.0–10 mol%), Ph₃P (3.0–10 mol%), and PhCOOH (3.0–10 mol%) in dry toluene (0.5 mL). The resulting suspension was stirred at the specified temperature under argon for 12 h. Upon completion of the reaction (monitored by TLC), the reaction mixture was diluted with EtOAc and then quenched with sat. aq NH₄Cl. The aqueous layer was extracted with EtOAc. The combined organic layers were dried (MgSO₄), filtered, concentrated in vacuo, and purified by flash chromatography to afford pure products 3. tert-Butyl 3-Allyl-2-oxo-3-o-tolylindoline-1-carboxylate (3b) ¹H NMR (400 MHz, CDCl₃): δ = 1.61 (s, 9 H), 2.31 (s, 3 H), 3.02 (m, 2 H), 4.97 (m, 2 H), 5.42 (m, 1 H), 7.12 (m, 2 H), 7.22 (m, 3 H), 7.36 (m, 1 H), 7.91 (d, J = 8.4 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.31, 28.25, 28.84, 42.59, 55.92, 88.26, 115.04, 119.79, 125.71, 127.68, 128.71, 129.09, 130.58, 134.12, 137.66, 139.64, 149.46, 176.55. HRMS (EI): m/z calcd for C₂₃H₂₅NNaO₃ [M + Na]⁺: 386.1729; found: 386.1727. tert-Butyl 3-Allyl-3-(2-methoxyphenyl)-2-oxoindoline-1-carboxylate (3c) ¹H NMR (400 MHz, CDCl₃): δ = 1.65 (s, 9 H), 3.01 (m, 2 H), 3.46 (s, 3 H), 4.97 (m, 2 H), 5.40 (m, 1 H), 6.78 (m, 2 H), 7.04 (m, 3 H), 7.23 (m, 1 H), 7.51 (m, 1 H), 7.81 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.31, 28.25, 28.84, 42.59, 55.92, 88.26, 115.04, 119.79, 125.71, 127.68, 128.71, 129.09, 130.58, 134.12, 137.66, 139.64, 149.46, 176.55. HRMS (EI): m/z calcd for C₂₃H₂₅NNaO₄ [M + Na]⁺: 402.1667; found: 402.1676. tert-Butyl 3-Allyl-2-oxo-3-m-tolylindoline-1-carboxylate (3d) ¹H NMR (400 MHz, CDCl₃): δ = 1.61 (s, 9 H), 2.31, (s, 3 H), 3.01 (m, 1 H), 3.11 (m, 1 H), 5.02 (m, 2 H), 5.40 (m, 1 H), 7.06 (m, 2 H), 7.21 (m, 4 H), 7.34 (m, 1 H), 7.93 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.56, 21.61, 27.96, 28.09, 28.16, 42.55, 56.61, 84.27, 115.09, 119.70, 124.25, 124.32, 125.16, 127.86, 128.39, 130.53, 131.95, 138.24, 139.18, 139.83, 149.28, 176.33. HRMS (EI): m/z calcd for C₂₀H₂₁NNaO₃ [M + Na]⁺: 346.1408; found: 346.1414.