A New Organocatalytic Process of Cyclotrimerization of Acetylenic Ketones Mediated by 2,4-Pentanedione

Abstract

A new organocatalytic process of cyclotrimerization of the aliphatic and aromatic acetylenic ketones was developed. The reaction catalyzed by DMAP in the presence of 2,4-pentanedione gave 1,3,5-trisubstituted benzenes in almost quantitative yields ­under very mild conditions. 2,4-Pentanedione was used as a co-­catalyst to promote the reaction efficiently, particularly for aliphatic acetylenic ketones.

Key words

acetylenic ketones - DMAP - cyclotrimerization - 2,4-pentanedione

References and Notes

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10

Typical Procedure.
A round-bottomed flask, equipped with a stirring bar, was charged with 2,4-pentanedione (0.15 mmol) and acetylenic ketone (0.3 mmol) dissolved in CH₂Cl₂ (2 mL) followed by DMAP (0.03 mmol). The reaction was run at r.t. for the indicated time (monitored by TLC). The reaction was concentrated under reduced pressure on a rotary evaporator and purified by silica gel chromatography using PE-EtOAc (10:1 to 3:1).
Compound 3a: ¹H NMR (300 MHz, CDCl₃): δ = 8.63 (s, 3 H), 2.64 (s, 9 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 196.7, 138.0, 131.8, 26.9 ppm. IR (KBr): ν = 1690, 1227 cm^-1. HRMS (EI): m/z calcd for C₁₂H₁₂O₃ [M]⁺: 204.0786; found: 204.0791.
Compound 3b: ¹H NMR (300 MHz, CDCl₃): δ = 8.56 (s, 3 H), 7.25-7.10 (m, 15 H), 3.31 (t, J = 7.5 Hz, 6 H), 3.03 (t, J = 7.5 Hz, 6 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 197.9, 140.8, 137.8, 131.3, 128.7, 128.6, 126.4, 40.8, 30.1 ppm. IR (KBr): ν = 1694, 1162 cm^-1. HRMS (EI): m/z calcd for C₃₃H₃₀O₃ [M]⁺: 474.2195; found: 474.2192.
Compound 6: ¹H NMR (300 MHz, CDCl₃): δ = 8.49 (d, J = 1.5 Hz, 2 H), 8.29 (d, J = 1.5 Hz, 1 H), 7.76 (d, J = 7.6 Hz, 4 H), 7.57-7.54 (m, 2 H), 7.47-7.42 (m, 4 H), 2.63 (s, 3 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 195.4, 193.9, 137.4, 136.4, 135.4, 133.8, 132.2, 131.5, 129.0, 127.6, 25.8 ppm. IR (KBr): ν = 1691, 1662, 1242 cm^-1. HRMS (EI): m/z calcd for C₂₂H₁₆O₃ [M]⁺: 328.1099; found: 328.1092.