Triphenylphosphine-Catalyzed Reaction of Aldehydes and Acetylenic Ketones with 1,3-Dicarbonyl Moieties: Synthesis of Multi-Carbonyl Compounds

Abstract

A mild and efficient domino process of aldehydes, ­acetylenic ketones and 1,3-dicarbonyl moieties catalyzed by tri­phenylphosphine is reported. The method supplies a facile way to synthesize multi-carbonyl compounds in moderate to good yields. A plausible mechanism is proposed for this domino reaction.

Key words

acetylenic ketones - PPh₃ - carbon-carbon bond formation - multi-carbonyl compounds

References

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12

Typical Procedure.
Benzaldehyde (0.3 mmol), 2,4-pentanedione (0.36 mmol) and phenyl acetylenic ketone (0.36 Lmol) were dissolved in 3 mL CH₂Cl₂. The mixture was cooled to 0 °C, and 20 mol% PPh₃ was added. The resulting mixture was warmed to r.t. and stirred for 6 h. After concentrated under reduced pressure the residue was purified by flash chromatography on silica gel (8:1 PE-EtOAc) to afford the corresponding pure product.
Compound 4a: mp 126-128 °C (lit.¹⁴ mp 126-127 °C). ¹H NMR (300 MHz, CDCl₃): δ = 8.01 (d, J = 7.2 Hz, 4 H), 7.58 (m, 2 H), 7.46 (m, 4 H), 5.38 (t, J = 6.8 Hz, 1 H), 3.97 (t, J = 6.8 Hz, 1 H), 2.51 (t, J = 6.8 Hz, 2 H), 2.27 (s, 6 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 204.4, 196.0, 135.6, 134.0, 129.1, 128.8, 64.8, 53.8, 29.8, 26.9 ppm. IR (neat): ν = 1725, 1696, 1671, 1596, 1580, 1253, 1181 cm^-1. HRMS (ESI): m/z calcd for C₂₁H₂₀O₄ [M + Na]⁺: 359.1254; found: 359.1255.
Compound 3a: ¹H NMR (300 MHz, CDCl₃): δ = 16.66 (s, 1 H), 7.78 (m, 2 H), 7.53 (m, 1 H), 7.45 (m, 2 H), 6.08 (s, 1 H), 6.04 (s, 1 H), 2.01 (s, 6 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 196.4, 191.1 (2 C), 143.5, 136.5, 133.4 133.3, 132.8, 130.7, 111.5, 23.9 (2 C) ppm. IR (neat): ν = 1710, 1657, 1333, 1255, 1198 cm^-1. HRMS (EI): m/z calcd for C₁₄H₁₄O₃ [M⁺]: 230.0943; found: 230.0947.