Palladium-Catalyzed Carbonyl-Retention Suzuki–Miyaura Coupling between N-Hydroxybenzotriazole Esters and Boronic Acids

Abstract

We have developed a palladium-catalyzed C–O bond activation of N-hydroxybenzotriazole esters, which represent a new type of electrophilic partner for Suzuki–Miyaura cross-coupling reactions to make various ketones. This reaction employed the cheap and commercially available PdCl₂(MeCN)₂/PCy₃ as the catalyst and proceeded at 80 °C.

Key words

palladium catalysis - Suzuki–Miyaura coupling - C–O bond activation - activated esters - ketone synthesis - N-hydroxybenzotriazole

Publication History

Received: 15 November 2022

Accepted after revision: 12 December 2022

Accepted Manuscript online:
12 December 2022

Article published online:
13 January 2023

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• 17 General Procedure for the Pd-Catalyzed Suzuki–Miyaura Coupling between AcOBt and Boronic Acid An oven-dried Schlenk tube was charged with a magnetic stir bar, PdCl₂(MeCN)₂ (2.59 mg, 0.02 mmol), PCy₃ (5.61 mg, 0.04 mmol), O-acyl N-hydroxybenzotriazole (0.2 mmol), boronic acid (1.5 equiv), and K₂CO₃ (2.0 equiv) under air. Then the Schlenk tube was capped with a rubber septum and connected to a Schlenk line. The Schlenk tube was evacuated and back filled with N₂ for three times before dioxane (2 mL) was added through a syringe. The perimeter of the septum was carefully sealed with parafilm. Next, the mixture was allowed for stirring at 80 °C in a metal sand bath for 12 h. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (5 mL), and the solvent was removed by a rotary evaporator. The crude product was purified by flash column chromatography (petroleum ether/ethyl acetate). Naphthalen-2-yl(phenyl)methanone (3l) The product was purified by flash column chromatography (petroleum ether/ethyl acetate = 200/1) as a white solid (30.4 mg, 66%), mp 82–84 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.27 (d, J = 1.3 Hz, 1 H), 7.98–7.84 (m, 6 H), 7.65–7.60 (m, 2 H), 7.59–7.49 (m, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 196.7, 137.9, 135.2, 134.8, 132.4, 132.2, 131.9, 130.1, 129.4, 128.3, 128.3, 128.3, 127.8, 126.8, 125.8. Furan-2-yl(phenyl)methanone (3m) The product was purified by flash column chromatography (petroleum ether/ethyl acetate = 300/1) as a white solid (14.9 mg, 43%), mp 43–45 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.02–7.93 (m, 2 H), 7.71 (d, J = 1.6 Hz, 1 H), 7.64–7.55 (m, 1 H), 7.49 (dd, J = 8.4, 7.0 Hz, 2 H), 7.23 (d, J = 3.6 Hz, 1 H), 6.59 (dd, J = 3.6, 1.7 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 182.5, 152.3, 147.1, 137.2, 132.6, 129.3, 128.4, 120.5, 112.2. Phenyl(thiophen-2-yl)methanone (3n) The product was purified by flash column chromatography (petroleum ether/ethyl acetate = 300/1) as a white solid (18.9 mg, 50%), mp 57–58 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.91–7.81 (m, 2 H), 7.72 (dd, J = 5.0, 1.2 Hz, 1 H), 7.65 (dd, J = 3.8, 1.2 Hz, 1 H), 7.62–7.56 (m, 1 H), 7.53–7.45 (m, 2 H), 7.16 (dd, J = 5.0, 3.8 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 188.2, 143.6, 138.1, 134.8, 134.2, 132.2, 129.1, 128.4, 127.9.
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