Expedient Synthesis of Terminal Vinylphosphonates by Palladium-Catalyzed C−C Cross-Coupling Reactions of (1-Halovinyl)phosphonates

Abstract

An efficient new synthetic route to (1-arylvinyl)phosphonates is presented. A wide range of (1-arylvinyl)phosphonates were prepared in good to excellent yields (79–99%) by using a palladium(II) acetate–organophosphine catalyst system. The protocol can be effectively scaled up without deleterious effects. The use of a (1-chloro­vinyl)phosphonate as the electrophilic coupling partner was demonstrated for the first time.

Key words

cross-coupling - phosphonates - palladium - catalysis - arylation

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• 16 Diethyl [1-(2-Tolyl)vinyl]phosphonate (3b); Typical Procedure A Schlenk flask was charged with phosphonate 2a (97.2 mg, 0.4 mmol), Pd(OAc)₂ (4.5 mg, 0.02 mmol), t-Bu₃P∙HBF₄ (11.6 mg, 0.04 mmol), 2-TolB(OH)₂ (81.6 mg, 0.6 mmol), and K₂CO₃ (138.0 mg, 1.0 mmol). The flask was evacuated for 10 min and then filled with N₂. Toluene (2.0 mL) was added, and the mixture was stirred at r.t. for 10 h. When the reaction as complete, the mixture was diluted with EtOAc (15.0 mL) and the catalyst and inorganic base were removed by filtration through a short pad of silica gel. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography [silica gel, PE–EtOAc (2:1)] to give a pale-yellow oil; yield: 92.5 mg (91%); IR (KBr): 3450, 2983, 2928, 1489, 1392, 1256, 1234, 1022, 962 cm^–1; ¹H NMR (500 MHz, CDCl₃): δ = 1.27 (t, J = 7.0 Hz, 6 H), 2.31 (s, 3 H), 4.04–4.10 (m, 4 H), 5.84 (dd, J = 2.0, 47.7 Hz, 1 H), 6.42 (dd, J = 22.6, 2.0 Hz, 1 H), 7.13–7.17 (m, 2 H), 7.20–7.21 (m, 2 H); ¹³C NMR (125 MHz, CDCl₃): δ = 16.3 (d, J = 6.4 Hz), 20.0, 62.2 (d, J = 6.1 Hz), 125.3 (d, J = 1.5 Hz), 127.8 (d, J = 1.8 Hz), 129.1 (d, J = 3.6 Hz), 130.2, 133.0 (d, J = 8.5 Hz), 136.0 (d, J = 5.4 Hz), 136.6 (d, J = 9.4 Hz), 140.0 (J = 175.8 Hz); ³¹P NMR (202.5 MHz, CDCl₃): δ = 16.0; GC/MS: m/z (%) 254 (27) [M⁺], 226 (11), 197 (48), 179 (5), 144 (4), 115 (100), 91 (12), 65 (8); HRMS (ESI): m/z [M + Na⁺] calcd for C₁₃H₁₉NaO₃P: 277.0970; found: 277.1004.