Catalytic Hydrophosphination of Alkenylalkyl Ethers

Abstract

Hydrophosphination of alkenylalkyl ethers catalyzed by Pd- and Ni-complexes is described. The reaction is regioselective giving only Markovnikov product isolated as α-alkoxyalkyldiphenyl oxide after oxidation by H₂O₂.

Key words

nickel - palladium - alkenes - hydrophosphination - al­kenylalkyl ethers

References

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15

Experimental Conditions: In a 8 mm tube filled with argon were placed Ni(PPh₃)₂Br₂ (55 mg, 5 mol%), Ph₂PH (279 mg, 1,5 mmol), alkenyl ether (1.65 mmol) and dry benzene (3 mL). The tube was sealed and placed in a hot bath. Reaction time and temperature are given in Table [2] . After cooling the tube was opened and the solvent was evaporated. The residue was dissolved in 15 mL of Et₂O and 2 ml 30% H₂O₂ was added. The mixture was stirred until the organic phase discoloured. The organic phase was separated, washed with water, dried under MgSO₄ and evaporated in vacuum. The target compound was recrystallized from hexane or purified by column chromatography (Al₂O₃, Et₂O). 1-Butoxy-ethyl(diphenyl)phosphine oxide (3a) was recrystallized from hexane (cooling up to -18 °C), colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 0.83-0.85 (t, 3 H), 1.22-1.26 (m, 2 H), 1.45-1.51 (m, 5 H), 3.19-3.25 (m, 1 H), 3.58-3.64 (m, 1 H), 4.19-4.23 (m, 1 H), 7.45-7.58 (m, 6 H), 7.88-7.92 (m, 2 H), 8.05-8.09 (m, 2 H). ³¹P{¹H} NMR (162.6 MHz, CDCl₃): δ = 30.0. Anal. Calcd: C, 71.52; H, 7.61. Found: C, 71.35; H, 7.45.