Base-Promoted Direct Oxyphosphorylation of Alkynes with H-Phosphine Oxides in the Presence of Water

Abstract

We have developed a simple method for the oxyphosphorylation of arylalkynes to give β-keto phosphine oxides without the assistance of any transition metal. An inorganic base promoted the oxyphosphorylation and water played a synergistic role in the formation of various β-keto phosphine oxides. The reaction showed a wide structural scope and broad functional-group tolerance, and it proceeded under mild reaction conditions. This method solved the problem of metal dependence in the oxyphosphorylation of alkynes, providing a potential application in organic chemistry. Control experiments revealed the mechanism of the oxyphosphorylation and the synergistic role played by water in the radical process.

Key words

alkynes - arylphosphorylalkanones - keto phosphine oxides - oxyphosphorylation - aralkynes

• References

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• 20 β-Keto Phosphonate Derivatives 3a–w; General Procedure A round-bottomed flask was charged with the appropriate alkyne 1 (0.25 mmol), H-phosphonate 2 (0.5 mmol), LiOH (0.05 mmol), DMF (2 mL), and H₂O (0.25 mL), and the mixture was stirred at 60 °C for 3 h under O₂ (balloon). When the reaction was complete, it was quenched with aq NaHCO₃ (20 mL) and the mixture was extracted with EtOAc (3 × 10 mL). The combined organic layers were washed with sat. brine (×2) then dried (MgSO₄), filtered, and concentrated in vacuum. The crude product was purified by chromatography [silica gel, CH₂Cl₂–MeOH (30:1 to 50:1)]. 2-(Diphenylphosphoryl)-1-phenylethanone (3a) White solid; yield: 68 mg (85%); mp 139.5–140.4 °C. ¹H NMR (400 MHz, CDCl₃): δ = 4.14 (d, J = 15.4 Hz, 2 H), 7.38–7.53 (m, 9 H), 7.78–7.83 (m, 4 H), 7.96–7.98 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 193.03 (d, J = 5.7 Hz), 137.13, 133.83, 132.52 (d, J = 2.8 Hz), 131.67 (d, J = 103.9 Hz), 131.32 (d, J = 9.7 Hz), 129.45, 128.85 (d, J = 12.3 Hz), 128.75, 43.52 (d, J = 58.2 Hz). ³¹P NMR (162 MHz, CDCl₃): δ = 27.16. HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₀H₁₇NaO₂P : 343.0858; found: 343.0861.