Synlett 2007(19): 3063-3067  
DOI: 10.1055/s-2007-992359
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© Georg Thieme Verlag Stuttgart · New York

Addition of Arylboronic Acids to Nitriles in Aqueous Media Catalyzed by a 2,2′-Bipyridine-Cyclopalladated Ferrocenylimine Complex

Ajuan Yu, Jingya Li, Mengjun Cui, Yangjie Wu*
Department of Chemistry, Key Lab of Chemical Biology and Organic Chemistry of Henan Province, Key and Open Lab of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P. R. of China
Fax: +86(371)67979408; e-Mail: wyj@zzu.edu.cn;
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Publikationsverlauf

Received 1 September 2007
Publikationsdatum:
08. November 2007 (online)

Abstract

The addition of arylboronic acids to nitriles catalyzed by a bipyridine-cyclopalladated ferrocenylimine complex in aqueous media was developed. The reactions could be conducted under acidic or basic conditions in aqueous media. The addition of NH4Cl was found to have a drastic effect on the reaction yields.

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General Procedure In a bottle was placed NH4Cl, which was then dried at 60 °C in vacuo for 6 h prior to use. A reaction vessel was charged with 0.5 mmol of benzonitrile, 1.5 mmol of PhB(OH)2, 3.0 mmol of NH4Cl, 0.5 mmol of sodium dodecyl sulfonate (SDS), Pd catalyst 2 in 2.0 mL of H2O incubated in a oil bath at 100 °C for 24 h. After cooling, the reaction mixture was diluted with 10 mL brine. The aqueous layer was extracted with CH2Cl2 and dried over Na2SO4. After evaporation of the solvent the residue was subjected to TLC (PE-CH2Cl2). The prepared compounds were identified by 1H NMR, 13C NMR, and MS. The new compound 3j was also identified by HRMS (ESI).
Selected Spectroscopic Data:
Catalyst 2: mp: 228-230 °C (dec.). 1H NMR (400 MHz, MeOD): δ = 2.12 (s, 3 H), 2.45 (s, 3 H), 4.36 (s, 5 H), 4.65 (t, J = 2.4 Hz, 1 H), 4.81 (d, J = 2.4 Hz, 1 H), 4.95 (d, J = 2.0 Hz, 1 H), 6.33 (d, J = 4.8 Hz, 1 H), 7.13 (t, J = 6.0 Hz, 3 H), 7.38 (d, J = 6.8 Hz, 2 H), 7.79 (t, J = 6.0 Hz, 1 H), 8.02 (t, J = 7.6 Hz, 1 H), 8.27 (t, J = 7.6 Hz, 1 H), 8.35 (d, J = 7.6 Hz, 1 H), 8.43 (d, J = 7.6 Hz, 1 H), 9.20 (d, J = 4.8 Hz, 1 H). 13C NMR (100 MHz, MeOD): δ = 17.3, 21.1, 70.6, 70.8, 72.2, 75.0, 92.1, 98.8, 124.2, 125.3, 127.3, 128.6, 131.8, 139.4, 141.4, 141.8, 145.5, 149.8, 154.1, 155.5, 157.8, 189.4. HRMS (ESI+): m/z calcd for C29H26N3FeClPd [M - Cl]+: 578.0511; found: 578.0518. IR (KBr): ν = 3018, 1633, 1600, 1473, 1438, 1368, 1227, 1153, 1106, 1073, 1027, 810, 776, 494 cm-1.
Compound 3a: 1H NMR (400 MHz, CDCl3): δ = 2.40 (s, 3 H), 4.26 (s, 2 H), 7.23-7.32 (m, 7 H), 7.91 (d, J = 7.4 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.7, 45.4, 126.8, 128.6, 128.8, 129.3, 129.4, 134.1, 134.8, 144.0, 197.3 ppm. MS (ESI+): m/z = 211.1 [M + H]+, 233.1 [M + Na]+, 249.0 [M + K]+.
Compound 3c: 1H NMR (400 MHz, CDCl3): δ = 3.86 (s, 3 H), 4.23 (s, 2 H), 6.91-6.94 (m, 2 H), 7.24-7.33 (m, 5 H), 7.98-8.00 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 45.3, 55.5, 113.8, 126.8, 128.6, 129.4, 129.7, 131.0, 135.0, 163.5, 196.2 ppm. MS (ESI+): m/z = 227.3 [M + H]+, 249.2 [M + Na]+, 265.2 [M + K]+.
Compound 3e: 1H NMR (400 MHz, CDCl3): δ = 4.27 (s, 2 H), 7.25-7.28 (m, 5 H), 7.32-7.36 (m, 2 H), 8.05-8.07 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 45.6, 120.3 (q, J = 257.4 Hz), 120.4, 127.1, 128.8, 129.4, 130.6, 134.1, 134.8, 152.7, 196.0 ppm. MS (ESI+): m/z = 281.0 [M + H]+, 303.1 [M + Na]+, 319.0 [M + K]+.
Compound 3f: 1H NMR (400 MHz, CDCl3): δ = 7.47 (t, J = 7.6 Hz, 4 H), 7.57 (t, J = 7.4 Hz, 2 H), 7.79-7.81 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 128.2, 130.0, 132.3, 137.5, 196.7 ppm. MS (ESI+): m/z = 183.1 [M + H]+, 205.1 [M + Na]+, 221.0 [M + K]+.
Compound 3j: 1H NMR (400 MHz, CDCl3): δ = 7.52-7.56 (m, 2 H), 7.66-7.70 (m, 1 H), 7.80-7.83 (m, 2 H), 8.00-8.04 (m, 2 H), 8.17-8.19 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 119.7 (q, J = 324.1 Hz), 128.8, 130.2, 130.7, 130.9, 133.8, 134.2, 135.9, 144.8, 194.6 ppm. MS (ESI+): m/z = 337.4 [M + Na]+, 353.7 [M + K]+. HRMS (ESI+): m/z calcd for C14H9F3SO3 [M + H]+: 315.0303; found: 315.0300.
Compound 3k: 1H NMR (400 MHz, CDCl3): δ = 6.92-6.96 (m, 2 H), 7.46-7.49 (m, 2 H), 7.55-7.59 (m, 1 H), 7.75-7.80 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 115.4, 128.3, 129.7, 129.9, 132.2, 133.1, 138.0, 160.6, 196.7 ppm. MS (ESI+): m/z = 199.2 [M + H]+, 221.1 [M + Na]+, 237.1 [M + K]+.
Compound 3l: 1H NMR (400 MHz, CDCl3): δ = 5.28 (s, 2 H), 6.94-7.01 (m, 3 H), 7.26-7.31 (m, 2 H), 7.48-7.52 (m, 2 H), 7.60-7.64 (m, 1 H), 8.00-8.02 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 70.8, 114.8, 121.7, 128.2, 128.8, 129.6, 133.9, 134.6, 158.0, 194.6 ppm. MS (ESI+): m/z = 213.1 [M + H]+, 235.0 [M + Na]+, 251.0 [M + K]+.
Compound 3m: 1H NMR (400 MHz, CDCl3): δ = 7.53 (t, J = 7.7, 2 H), 6.64-7.68 (m, 1 H), 7.79-7.81 (m, 2 H), 7.93-7.96 (m, 2 H), 8.33-8.36 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 123.6, 128.7, 130.1, 130.7, 133.5, 136.3, 142.9, 149.9, 194.8 ppm. MS (ESI+): m/z = 228.4 [M + H]+, 250.3 [M + Na]+.