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
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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 CH2 Cl2 (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 : 1 H NMR (300 MHz, CDCl3 ): δ = 8.63 (s, 3 H), 2.64 (s, 9 H) ppm. 13 C 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 C12 H12 O3 [M]+ : 204.0786; found: 204.0791. Compound 3b : 1 H 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. 13 C 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 C33 H30 O3 [M]+ : 474.2195; found: 474.2192. Compound 6 : 1 H 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. 13 C 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 C22 H16 O3 [M]+ : 328.1099; found: 328.1092.