Regioselective Three-Component Coupling by the Palladium-Catalyzed Reaction of 2-Fluoroallylic Acetates with Phenols and Imides

Abstract

A palladium-catalyzed three-component coupling reaction of 2-fluoroallylic acetates with phenols, and imides is disclosed. The reaction was effectively catalyzed by [Pd(C₃H₅)Cl]₂/DPPF in the presence of Cs₂CO₃, and phenols and imides were introduced onto the allyl unit through the C–F bond activation. Furthermore, the reaction proceeds with both high regioselectivity and high Z-selectivity.

Key words

coupling - fluorine - imides - palladium - phenols

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• 9 Palladium-Catalyzed Reaction of 2-Fluoroallylic Acetates 1, 2, and 3 A typical procedure is given for the reaction of 2-fluorocinnamyl acetate (1a), succinimide (2a), and phenol (3a, Table 1, entry 7). To a solution of [Pd(π-allyl)Cl]₂ (2.4 mg, 0.0065 mmol), DPPF (7.2 mg, 0.013 mmol), succinimide (2a, 58 mg, 0.59 mmol), phenol (3a, 49 mg 0.52 mmol), and Cs₂CO₃ (169 mg, 0.52 mmol) in toluene (0.8 mL) was added (Z)-2-fluoro-3-phenylallyl acetate (1a, 25 mg, 0.13 mmol) at r.t., then stirred at 80 °C for 16 h. The reaction mixture was quenched with H₂O and extracted with Et₂O (3 × 2 mL). The combined organic layers were dried over MgSO₄ and concentrated in vacuo. The residue was chromatographed on silica gel (hexane–EtOAc, 60:40) to give 34 mg (84%) of 4aaa, which is a mixture of two stereoisomers, as a white solid. The pure major stereoisomer (Z isomer) was obtained after recrystallization from CH₂Cl₂–hexane (1:5) at r.t.; mp 106–108 °C. ¹H NMR (270 MHz, CDCl₃): δ = 2.49 (s, 4 H), 4.34 (s, 2 H), 6.30 (s, 1 H), 6.96–7.05 (m, 3 H), 7.15–7.31 (m, 5 H), 7.51 (dd, J = 8.4, 1.6 Hz, 2 H). Selected ¹H NMR of minor isomer (E)-4aaa: δ = 2.54 (s, 4 H), 4.59 (s, 2 H), 6.00 (s, 1 H), aromatic region overlaps with major isomer. ¹³C NMR (67.5 MHz, CDCl₃): δ = 28.0, 41.0, 116.2, 120.0, 122.7, 127.7, 128.4, 128.8, 129.6, 133.5, 144.3, 155.2, 176.4. IR (KBr) 3063, 3022, 1955, 1448, 1255, 1059, 1023, 1006, 879, 568, 515, 493 cm^–1. ESI-HRMS: m/z calcd for C₁₉H₁₇NNaO₃ [M + Na]⁺: 330.1106; found: 330.1102.
• 10 We also examined the reaction with alcohols, such as t-BuOH, and confirmed that detectable amount of linear type allylic imidated products was obtained instead of doubly substituted products.
• 11 The structure was confirmed by X-ray crystallographic analysis. CCDC 1516045 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. Please see the Supporting Information for details.