Nickel-Catalyzed O-Methylation of Cinnamic Acid Using DMSO as Methyl Surrogate

Abstract

A new method for the O-methylation of cinnamic acid employing DMSO as the methylating agent has been devised, employing a Ni-DMAP complex as catalyst along with Ag₂O and dimethylamine as additives. This protocol demonstrates broad substrate compatibility and good tolerance towards various functional groups. The key advantages of this approach include the utilization of cost-effective catalysts, moderate to high yield of the products, and short reaction time.

Key words

cinnamic acid - methylation - DMSO - Ag₂O - diethylamine - Ni-DMAP catalyst

• References and Notes

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• 22 Representative Procedure for the O-Methylation of Cinnamic Acid In a Schlenk tube containing 2 mL of DMSO, cinnamic acid (148 mg, 1 mmol), diethylamine (414 mL, 4 mmol), Ag₂O (460 mg, 2 mmol), and catalyst (3 mol%) were added with constant stirring. The tube containing the reaction mixture was then kept under heating in an oil bath at 120 °C for 12 h. The reaction mixture was quenched by 30 mL of water and extracted by using ethyl acetate (3 × 20 mL). The combined organic phase was then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography over silica gel using a mixture of ethyl acetate (10%) and petroleum ether (90%) to furnish the pure methyl cinnamate. (E)-Methyl 3-(3-Chloro-4-methoxyphenyl)acrylate White solid; 0.161 g (72%) yield; mp 84–86 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.59 (s, 1 H), 7.55 (s, 1 H), 7.39–7.36 (m, 1 H), 6.91 (d, J = 12.0 Hz, 1 H), 6.30 (d, J = 16.0 Hz, 1 H), 3.92 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 167.3, 156.4, 143.1, 129.3, 128.1, 127.8, 123.8, 123.1, 116.6, 111.9, 56.1, 51.6. HRMS (ESI): m/z calcd for C₁₁H₁₂ClO₃ ⁺: 227.0470 [M + H]⁺; found: 227.047. (E)-Methyl 3-(5-Bromo-2-fluorophenyl)acrylate White solid; 0.174 g (68%) yield, mp 70–72 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.72–7.68 (m, 1 H), 7.63–7.62 (m, 1 H), 7.44–7.42 (m, 1 H), 7.00–6.96 (m, 1 H), 6.52–6.49 (m, 1 H), 3.8 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 166.6, 160.9, 135.7, 134.1 (J_CF = 8.8 Hz), 131.3 (J_CF = 1.4 Hz), 124.3 (J _CF = 8.8 Hz), 121.5 (J _CF = 4.3 Hz), 117.9 (J _CF = 15.4 Hz), 116.9 (J _CF = 2.2 Hz), 51.8. HRMS (ESI): m/z calcd for C₁₀H₉BrFO₂ ⁺: 258.9765 [M + H]⁺; found: 258.9757. (E)-Methyl 3-(Benzo[d][1,3]dioxol-5-yl)acrylate White solid; 0.164 g (80%) yield; mp 66–68 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.60 (d, J = 12.0 Hz, 1 H), 7.03–6.99 (m, 2 H), 6.81 (d, J = 5.6 Hz, 1 H), 6.26 (d, J = 10.8 Hz, 1 H), 6.00 (s, 2 H), 3.79 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 167.5, 149.5, 148.3, 144.5, 128.7, 124.4, 115.6, 108.5, 106.4, 101.5, 51.6.