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

doi:10.1055/s-2007-992359

LETTER

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;

Abstract

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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.

Key words

cyclopalladated ferrocenylimine complex - arylboronic acids - nitriles - bipyridine - catalysis

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References

References and Notes

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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]⁺.