High Surface Area CeO2 Promoted Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and Aryl Iodides

Marilyn Graziano Mayer; Fabiana Nador; María Alicia Volpe; Gabriel Radivoy

doi:10.1055/s-0032-1318111

Synlett, Table of Contents

Synlett 2013; 24(3): 338-342
DOI: 10.1055/s-0032-1318111

letter

High Surface Area CeO₂ Promoted Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and Aryl Iodides

Marilyn Graziano Mayer

^aInstituto de Química del Sur, INQUISUR (CONICET-UNS), Departamento de Química, Universidad Nacional del Sur, Avenida Alem 1253, 8000 Bahía Blanca, Argentina Fax: +54(291)4595187 Email: gradivoy@criba.edu.ar

,

Fabiana Nador

^aInstituto de Química del Sur, INQUISUR (CONICET-UNS), Departamento de Química, Universidad Nacional del Sur, Avenida Alem 1253, 8000 Bahía Blanca, Argentina Fax: +54(291)4595187 Email: gradivoy@criba.edu.ar

,

María Alicia Volpe

^bPlanta Piloto de Ingeniería Química, PLAPIQUI (CONICET-UNS), Camino La Carrindanga Km 7, CC 717, 8000 Bahía Blanca, Argentina

,

Gabriel Radivoy*

^aInstituto de Química del Sur, INQUISUR (CONICET-UNS), Departamento de Química, Universidad Nacional del Sur, Avenida Alem 1253, 8000 Bahía Blanca, Argentina Fax: +54(291)4595187 Email: gradivoy@criba.edu.ar

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Abstract

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Abstract

High surface area cerium oxide (240 m²/g) efficiently promoted the Suzuki–Miyaura cross-coupling of aryl iodides with arylboronic acids, in the absence of palladium or any other transition-metal catalyst. Excellent selectivity towards the cross-coupling product was observed. Cerium oxide could be recovered and reused at least three times without any loss of activity.

Key words

biaryls - cross-coupling - cerium oxide - Suzuki–Miyaura reaction - palladium-free

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References

References and Notes

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11 Typical Experimental Procedure: High surface area CeO₂ (250 mg, 240 m²/g, Rhône-Poulenc) was calcined inside the reaction flask prior to use. The calcination treatment consisted in heating by means of a heat gun (160 ºC) under vacuum (0.1 Torr) for 5 min. Once the reaction flask reached r.t., the corresponding boronic acid (1 mmol) and K₂CO₃ (2 mmol, 276 mg) were added together with DMF (2 mL). The reaction vessel was immersed in a pre-heated silicon oil bath at 150 ºC. After stirring the mixture at this temperature for 5 min, a solution of the aryl halide (0.7 mmol) in DMF (1 mL) was added. The reaction progress was monitored by GC–MS. The resulting suspension was diluted with Et₂O (10 mL) and filtered by Büchner funnel. The filtrate was evaporated (15 Torr) and the resulting residue was purified by flash column chromatography (silica gel, hexane–EtOAc) to afford the corresponding biaryl product. The following known compounds included in Table 2 were characterized by comparison of their chromatographic and spectroscopic data (¹H NMR, ¹³C NMR, and MS) with those described in the literature: (1,1′-biphenyl)-4-carbonitrile (3ab; ref 13), 4-(trifluoromethyl)-1,1′-biphenyl (3ac; ref 14), 4-methyl-1,1′-biphenyl (3aa; ref 15), 4-methoxy-1,1′-biphenyl (3ad; ref 15), 4-chloro-1,1′-biphenyl (3ae; ref 15), 4-fluoro-1,1′-biphenyl (3af; ref 14), 4-methoxy-4′-methyl-1,1′-biphenyl (3ba; ref 16), N,N-4′-trimethyl-(1,1′-biphenyl)-4-amine (3ca; ref 15).

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